Composite oxide comprising In and Zn, and transistor

ABSTRACT

A novel material and a transistor using a novel material are provided. A composite oxide includes at least two regions, one of which includes In, Zn and an element M1 (the element M1 is one or more of Al, Ga, Si, B, Y, Ti, Fe, Ni, Ge, Zr, Mo, La, Ce, Nd, Hf, Ta, W, Mg, V, Be, and Cu), and the other of which includes In, Zn, and an element M2 (the element M2 is one or more of Al, Ga, Si, B, Y, Ti, Fe, Ni, Ge, Zr, Mo, La, Ce, Nd, Hf, Ta, W, Mg, V, Be, and Cu). The proportion of the element M1 to In, Zn, and the element M1 in the region including the element M1 is less than that of the element M2 to In, Zn, and the element M2 in the region including the element M2. In an analysis of the composite oxide by X-ray diffraction, the diffraction pattern result in the X-ray diffraction is asymmetric with the angle at which the peak intensity of X-ray diffraction is detected as the symmetry axis.

TECHNICAL FIELD

The present invention relates to an object, a method, or a manufacturingmethod. The present invention also relates to a process, a machine,manufacture, or a composition of matter. In particular, one embodimentof the present invention relates to a metal oxide or a manufacturingmethod of the metal oxide. One embodiment of the present invention alsorelates to a semiconductor device, a display device, a liquid crystaldisplay device, a light-emitting device, a power storage device, amemory device, a method for driving them, or a method for manufacturingthem.

In this specification and the like, a semiconductor device generallymeans a device that can function by utilizing semiconductorcharacteristics. A semiconductor element such as a transistor, asemiconductor circuit, an arithmetic device, and a memory device areeach an embodiment of the semiconductor device. An imaging device, adisplay device, a liquid crystal display device, a light-emittingdevice, an electro-optical device, a power generation device, (includinga thin film solar cell, an organic thin film solar cell, and the like),and an electronic device may each include a semiconductor device.

BACKGROUND ART

A technique in which a transistor is fabricated using an In—Ga—Zn-basedmetal oxide is disclosed (for example, see Patent Document 1).

Non-Patent Document 1 discusses a structure in which an active layer ofa transistor includes two layers of metal oxides of an In—Zn oxide andan In—Ga—Zn oxide.

REFERENCES Patent Document

-   [Patent Document 1] Japanese Published Patent Application No.    2007-96055

Non-Patent Document

-   [Non-Patent Document 1] John F. Wager, “Oxide TFTs: A Progress    Report”, Information Display 1/16, SID 2016, January/February 2016,    Vol. 32, No. 1, pp. 16-21

SUMMARY OF THE INVENTION Problems to be Solved by the Invention

In Non-Patent Document 1, a channel-protective bottom-gate transistorincludes a two-layer stack of indium zinc oxide and IGZO as an activelayer and sets the thickness of the indium zinc oxide where a channel isformed to 10 nm, thereby achieving a high field-effect mobility (μ=62cm²V⁻¹s⁻¹). However, the S value (the subthreshold swing, also referredto as SS), which is one of transistor characteristics, is as large as0.41 V/decade. Moreover, the threshold voltage (Vth), which is also oneof transistor characteristics, is −2.9 V, which means that thetransistor has a normally-on characteristic.

In view of the above problems, an object of one embodiment of thepresent invention is to provide a novel metal oxide. Another object ofone embodiment of the present invention is to give favorable electricalcharacteristics to a semiconductor device. Another object of oneembodiment of the present invention is to provide a highly reliablesemiconductor device. Another object of one embodiment of the presentinvention is to provide a semiconductor device with a novel structure.Another object of one embodiment of the present invention is to providea display device with a novel structure.

Note that the description of these objects does not disturb theexistence of other objects. In one embodiment of the present invention,there is no need to achieve all the objects. Other objects will beapparent from and can be derived from the description of thespecification, the drawings, the claims, and the like.

Means for Solving the Problems

One embodiment of the present invention is a composite oxide includingat least two regions. One of the regions includes In, Zn and an elementM1 (the element M1 is one or more of Al, Ga, Si, B, Y, Ti, Fe, Ni, Ge,Zr, Mo, La, Ce, Nd, Hf, Ta, W, Mg, V, Be, and Cu), and the other regionincludes In, Zn, and an element M2 (the element M2 is one or more of Al,Ga, Si, B, Y, Ti, Fe, Ni, Ge, Zr, Mo, La, Ce, Nd, Hf, Ta, W, Mg, V, Be,and Cu). The proportion of the element M1 to In, Zn, and the element M1in the region including the element M1 is less than the proportion ofthe element M2 to In, Zn, and the element M2 in the region including theelement M2. In an analysis of the composite oxide by X-ray diffraction,the diffraction pattern result in the X-ray diffraction is asymmetricwith the angle at which the peak intensity of X-ray diffraction isdetected as the symmetry axis.

In the above embodiment, the peak intensity is detected between 2θ=30°and 2θ=35°.

In the above embodiment, the element M1 and the element M2 are Ga.

One embodiment of the present invention is a transistor including theabove-described composite oxide, a gate, a source, and a drain. Thecomposite oxide is used as a channel region in the transistor.

Effect of the Invention

According to one embodiment of the present invention, a novel metaloxide can be provided. According to another embodiment of the presentinvention, favorable electrical characteristics can be given to asemiconductor device. According to another embodiment of the presentinvention, a highly reliable semiconductor device can be provided.According to another embodiment of the present invention, asemiconductor device with a novel structure can be provided. Accordingto another embodiment of the present invention, a display device with anovel structure can be provided.

Note that the description of these effects does not disturb theexistence of other effects. One embodiment of the present invention doesnot necessarily achieve all the effects. Other effects will be apparentfrom and can be derived from the description of the specification, thedrawings, the claims, and the like.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 A conceptual view of a composition of a metal oxide.

FIGS. 2A-2C Schematic views showing a transistor and distribution ofenergy levels in the transistor.

FIGS. 3A-3C Views showing a model of a schematic band diagram of atransistor.

FIGS. 4A-4C Views showing a model of a schematic band diagram of atransistor.

FIGS. 5A-5C Views showing a model of a schematic band diagram of atransistor.

FIGS. 6A-6C A top view and cross-sectional views showing a semiconductordevice.

FIGS. 7A-7C A top view and cross-sectional views showing a semiconductordevice.

FIGS. 8A-8B Cross-sectional views showing a semiconductor device.

FIGS. 9A-9D Cross-sectional views showing a method for manufacturing asemiconductor device.

FIGS. 10A-10C Cross-sectional views showing a method for manufacturing asemiconductor device;

FIGS. 11A-11C Cross-sectional views showing a method for manufacturing asemiconductor device.

FIGS. 12A-12C A top view and cross-sectional views showing asemiconductor device.

FIGS. 13A-13C A top view and cross-sectional views showing asemiconductor device.

FIGS. 14A-14C A top view and cross-sectional views showing asemiconductor device.

FIGS. 15A-15C A top view and cross-sectional views showing asemiconductor device.

FIGS. 16A-16C Views showing an atomic ratio range of a metal oxide ofthe present invention.

FIG. 17 A view showing a structure example of a display panel.

FIG. 18 A view showing a structure example of a display panel.

FIGS. 19A-19B Views showing a model of a metal oxide of one embodimentand its density of states.

FIGS. 20A-20D Views showing local structures of models of metal oxidesto which impurities are added in one embodiment and their densities ofstates.

FIGS. 21A-21D Views showing local structures of models of metal oxidesto which impurities are added in one embodiment and their densities ofstates.

FIGS. 22A-22D Views showing local structures of models of metal oxidesto which impurities are added in one embodiment and their densities ofstates.

FIGS. 23A-23C Graphs showing the proportion of each kind of atomsobtained by using XPS measurement results of samples of Example.

FIG. 24 Graphs showing measured XRD spectra of samples of Example.

FIG. 25 A view showing an apparatus used for measurement of a sample ofExample.

FIG. 26 A graph showing measured XRD spectra of samples of Example.

FIGS. 27A-27D Graphs showing measured XRD spectra of samples of Example.

FIGS. 28A-28D Graphs showing measured XRD spectra of samples of Example.

FIGS. 29A-29F Cross-sectional TEM images and electron diffractionpatterns of samples of Example.

FIGS. 30A-30L A plan-view TEM image, a cross-sectional TEM image, andelectron diffraction patterns of samples of Example.

FIG. 31 Plan-view TEM images of samples of Example and images obtainedthrough analysis thereof.

FIGS. 32A-32D Views showing a method for deriving a rotation angle of ahexagon.

FIGS. 33A-33E Views showing a method for forming a Voronoi diagram.

FIG. 34 Graphs showing the numbers of shapes of Voronoi regions ofExample and proportions thereof.

FIGS. 35A-35H Plan-view TEM images, cross-sectional TEM images, and EDXmapping images of samples of Example.

FIGS. 36A-36F EDX mapping images of samples of Example.

FIG. 37 Graphs showing I_(d)-V_(g) characteristics of samples ofExample.

FIG. 38 Graphs showing I_(d)-V_(g) characteristics of samples after +GBTstress tests of Example.

FIGS. 39A-39B Graphs showing I_(d)-V_(g) characteristics and I_(d)-V_(d)characteristics of a transistor.

FIG. 40 A graph showing I_(d)-V_(g) characteristics and linear andsaturation mobility curves which are calculated on the basis of GCA.

FIGS. 41A-41F Cross-sectional TEM images and electron diffractionpatterns of samples of Example.

FIGS. 42A-42F Plan-view TEM images of samples of Example and imagesobtained through analysis thereof.

FIGS. 43A-43C Graphs showing the numbers of shapes of Voronoi regions ofExample and proportions thereof.

FIGS. 44A-44H Plan-view TEM images, cross-sectional TEM images, and EDXmapping images of samples of Example.

FIGS. 45A-45C EDX mapping images of a sample of Example.

FIGS. 46A-46H Plan-view TEM images, cross-sectional TEM images, and EDXmapping images of samples of Example.

FIG. 47 Graphs showing I_(d)-V_(g) characteristics of samples ofExample.

FIGS. 48A-48D A cross-sectional TEM image, EDX mapping images, and agraph showing an atomic ratio of a sample of Example.

FIGS. 49A-49D A plan-view TEM image, EDX mapping images, and a graphshowing an atomic ratio of a sample of Example.

FIG. 50 A graph showing I_(d)-V_(g) characteristics.

FIG. 51 A graph showing I_(d)-V_(g) characteristics.

FIG. 52 A graph showing calculation results of a density of interfacestates.

FIGS. 53A-53B Graphs showing I_(d)-V_(g) characteristics.

FIG. 54 Graphs showing calculation results of a density of defectstates.

FIG. 55 Graphs showing calculation results of a density of defectstates.

FIG. 56 A graph showing I_(d)-V_(g) characteristics of a transistor.

MODE FOR CARRYING OUT THE INVENTION

Embodiments will be described below with reference to drawings. Notethat embodiments can be carried out in many different modes, and it iseasily understood by those skilled in the art that modes and details ofthe present invention can be modified in various ways without departingfrom the spirit and the scope of the present invention. Thus, thepresent invention should not be interpreted as being limited to thefollowing description of the embodiments.

In the drawings, the size, the layer thickness, or the region isexaggerated for clarity in some cases. Therefore, the size, the layerthickness, or the region is not limited to the illustrated scale. Notethat the drawings are schematic views showing ideal examples, andembodiments of the present invention are not limited to shapes, values,or the like shown in the drawings.

Note that in this specification, ordinal numbers such as “first”,“second”, and “third” are used in order to avoid confusion amongcomponents, and the terms do not limit the components numerically.

In this specification, terms for describing arrangement, such as “over”and “under”, are used for convenience in describing a positionalrelationship between components with reference to drawings. Furthermore,the positional relationship between components changes as appropriate inaccordance with the direction in which each component is described.Thus, one embodiment of the present invention is not limited to termsused in this specification, and the terms can be changed appropriatelydepending on the situation.

In this specification and the like, a transistor is an element having atleast three terminals of a gate, a drain, and a source. The transistorhas a channel region between the drain (a drain terminal, a drainregion, or a drain electrode) and the source (a source terminal, asource region, or a source electrode), and current can flow between thesource and the drain through the channel region. Note that in thisspecification and the like, a channel region refers to a region throughwhich current mainly flows.

Furthermore, functions of a source and a drain might be switched when atransistor of opposite polarity is employed or a direction of currentflow is changed in circuit operation, for example. Therefore, the terms“source” and “drain” can be used interchangeably in this specificationand the like.

In this specification and the like, the term “electrically connected”includes the case where components are connected through an “objecthaving any electric function”. There is no particular limitation on an“object having any electric function” as long as electric signals can betransmitted and received between components that are connected throughthe object. Examples of the “object having any electric function”include a switching element such as a transistor, a resistor, aninductor, a capacitor, and an element with a variety of functions aswell as an electrode and a wiring.

In this specification and the like, a silicon oxynitride film refers toa film that includes oxygen at a higher proportion than nitrogen, and asilicon nitride oxide film refers to a film that includes nitrogen at ahigher proportion than oxygen.

In the description of components of the invention in this specificationand the like with reference to the drawings, the same components indifferent drawings are denoted by the same reference numeral in somecases.

In this specification and the like, the term “parallel” indicates thatthe angle formed between two straight lines is greater than or equal to−10° and less than or equal to 10°. Thus, the case where the angle isgreater than or equal to −5° and less than or equal to 5° is alsoincluded. In addition, the term “substantially parallel” indicates thatthe angle formed between two straight lines is greater than or equal to−30° and less than or equal to 30°. The term “perpendicular” indicatesthat the angle formed between two straight lines is greater than orequal to 80° and less than or equal to 100°. Thus, the case where theangle is greater than or equal to 85° and less than or equal to 95° isalso included. In addition, the term “substantially perpendicular”indicates that the angle formed between two straight lines is greaterthan or equal to 60° and less than or equal to 120°.

In this specification and the like, the terms “film” and “layer” can beinterchanged with each other depending on the case. For example, theterm “conductive layer” can be changed into the term “conductive film”in some cases. Also, for example, the term “insulating film” can bechanged into the term “insulating layer” in some cases.

Note that a “semiconductor” includes characteristics of an “insulator”in some cases when the conductivity is sufficiently low, for example.Furthermore, a “semiconductor” and an “insulator” cannot be strictlydistinguished from each other in some cases because a bordertherebetween is not clear. Accordingly, a “semiconductor” described inthis specification can be called an “insulator” in some cases.Similarly, an “insulator” described in this specification can be calleda “semiconductor” in some cases.

Note that in this specification and the like, In:Ga:Zn=4:2:3 or aneighborhood of In; Ga:Zn=4:2:3 refers to an atomic ratio where, when Inis 4 with respect to the total number of atoms, Ga is greater than orequal to 1 and less than or equal to 3 (1≤Ga≤3) and Zn is greater thanor equal to 2 and less than or equal to 4 (2≤Zn≤4). In:Ga:Zn=5:1:6 or aneighborhood of In:Ga:Zn=5:1:6 refers to an atomic ratio where, when Inis 5 with respect to the total number of atoms, Ga is greater than 0.1and less than or equal to 2 (0.1<Ga≤2) and Zn is greater than or equalto 5 and less than or equal to 7 (5≤Zn≤7). In:Ga:Zn=1:1:1 or aneighborhood of In; Ga:Zn=1:1:1 refers to an atomic ratio where, when Inis 1 with respect to the total number of atoms, Ga is greater than 0.1and less than or equal to 2 (0.1<Ga≤2) and Zn is greater than 0.1 andless than or equal to 2 (0.1<Zn≤2).

Embodiment 1

In this embodiment, a composite oxide of one embodiment of the presentinvention will be described. Note that the composite oxide is an oxidehaving a cloud-aligned composite (CAC) composition. Examples of thecomposite oxide include a metal oxide containing a plurality of metalelements.

In this specification, the composite oxide which is one embodiment ofthe present invention is defined as a CAC-OS (oxide semiconductor) whenhaving a semiconductor function.

The CAC-OS or the CAC-metal oxide is referred to as a matrix compositeor a metal matrix composite in some cases.

The composite oxide of one embodiment of the present inventionpreferably contains at least indium. In particular, indium and zinc arepreferably contained. In addition, an element M (the element M is one ormore elements selected from aluminum, gallium, yttrium, copper,vanadium, beryllium, boron, silicon, titanium, iron, nickel, germanium,zirconium, molybdenum, lanthanum, cerium, neodymium, hafnium, tantalum,tungsten, magnesium, and the like) may be contained.

The composite oxide of one embodiment of the present inventionpreferably contains nitrogen. Specifically, the nitrogen concentrationin the composite oxide of one embodiment of the present inventionmeasured by SIMS may be 1×10¹⁶ atoms/cm³ or higher, preferably 1×10¹⁷atoms/cm³ or higher and 2×10²² atoms/cm³ or lower. Note that a compositeoxide to which nitrogen is added tends to have a smaller band gap andthus have improved conductivity. Thus, in this specification and thelike, the composite oxide of one embodiment of the present inventionincludes a composite oxide to which nitrogen or the like is added.Moreover, a composite oxide containing nitrogen may be referred to as acomposite oxynitride (metal oxynitride).

Here, the case where the composite oxide contains indium, the element M,and zinc is considered. The terms of the atomic ratio of indium to theelement M and zinc contained in the composite oxide are denoted by [In],[M], and [Zn], respectively.

<Composition of Composite Oxide>

A conceptual view of a metal oxide which is a composite oxide having aCAC composition of the present invention is illustrated in FIG. 1 .

For example, in the CAC-OS, as illustrated in FIG. 1 , elementsconstituting a metal oxide are unevenly distributed over a substrate(described as Sub. in FIG. 1 ), and regions 001 mainly including anelement and regions 002 mainly including another element are formed. Theregions 001 and 002 are mixed to form a mosaic pattern. In other words,the CAC-OS has a composition of a material in which elementsconstituting the metal oxide are unevenly distributed with a sizegreater than or equal to 0.5 nm and less than or equal to 10 nm,preferably less than or equal to 3 nm, or a similar size. Note that inthe following description, a mosaic pattern or a patch-like pattern of ametal oxide refers to a state in which one or more metal elements areunevenly distributed and regions which include the metal element andeach have a size of greater than or equal to 0.5 nm and less than orequal to 10 nm, preferably less than or equal to 3 nm, or a similar sizeare mixed.

For example, an In-M-Zn oxide with the CAC composition has a compositionin which materials are separated into an indium oxide (hereinafterreferred to as InO_(X1) (X1 is a real number greater than 0)) or anindium zinc oxide (hereinafter referred to as In_(X2)Zn_(Y2)O_(Z2) (X2,Y2, and Z2 are real numbers greater than 0)), an oxide including theelement M, and the like, and thus a mosaic pattern is formed. In thecomposition, InO_(X1) or In_(X2)Zn_(Y2)O_(Z2) forming the mosaic patternis distributed in the film (hereinafter also referred to as a cloud-likecomposition). Note that in this specification, a slight amount ofgallium (Ga) may be mixed in the separated InO_(X1) orIn_(X2)Zn_(Y2)O_(Z2) so that a solid solution state is formed.

In other words, the metal oxide of one embodiment of the presentinvention includes at least two or more oxides or materials selectedfrom an In oxide, an In-M oxide, an M oxide, an M-Zn oxide, an In—Znoxide, and an In-M-Zn oxide.

Typically, the metal oxide of one embodiment of the present inventionincludes at least two or more oxides selected from an In oxide, an In—Znoxide, an In—Al—Zn oxide, an In—Ga—Zn oxide, an In—Y—Zn oxide, anIn—Cu—Zn oxide, an In—V—Zn oxide, an In—Be—Zn oxide, an In—B—Zn oxide,an In—Si—Zn oxide, an In—Ti—Zn oxide, an In—Fe—Zn oxide, an In—Ni—Znoxide, an In—Ge—Zn oxide, an In—Zr—Zn oxide, an In—Mo—Zn oxide, anIn—La—Zn oxide, an In—Ce—Zn oxide, an In—Nd—Zn oxide, an In—Hf—Zn oxide,an In—Ta—Zn oxide, an In—W—Zn oxide, and an In—Mg—Zn oxide. That is, themetal oxide of one embodiment of the present invention can be referredto as a composite metal oxide including a plurality of materials or aplurality of components.

Here, let a concept in FIG. 1 illustrate an In-M-Zn oxide with the CACcomposition. In this case, it can be said that the region 001 is aregion including an oxide including the element M as a main componentand the region 002 is a region including In_(X2)Zn_(Y2)O_(Z2) orInO_(X1) as a main component. At this time, surrounding portions of theregion including an oxide including the element M as a main component,the region including In_(X2)Zn_(Y2)O_(Z2) or InO_(X1) as a maincomponent, and a region including at least Zn are unclear (blurred), sothat boundaries are not clearly observed in some cases.

In other words, an In-M-Zn oxide with the CAC composition is a metaloxide in which a region including an oxide including the element M as amain component and a region including In_(X2)Zn_(Y2)O_(Z2) or InO_(X1)as a main component are mixed. Accordingly, the metal oxide is referredto as a composite metal oxide in some cases. Note that in thisspecification, for example, when the atomic ratio of In to the element Min the region 002 is greater than the atomic ratio of In to the elementM in the region 001, the region 002 has higher In concentration than theregion 001.

Note that in the metal oxide having the CAC composition, a stacked-layerstructure including two or more kinds of films with differentcompositions is not included. For example, a two-layer structure of afilm including In as a main component and a film including Ga as a maincomponent is not included.

Specifically, a CAC-OS in an In—Ga—Zn oxide (an In—Ga—Zn oxide in theCAC-OS may be particularly referred to as CAC-IGZO) is described. In theCAC-OS in the In—Ga—Zn oxide, materials are separated into InO_(X1) orIn_(X2)Zn_(Y2)O_(Z2) and an oxide including gallium, for example, and amosaic pattern is formed. InO_(X1) or In_(X2)Zn_(Y2)O_(Z2) with themosaic pattern is a cloud-like metal oxide.

In other words, the CAC-OS in the In—Ga—Zn oxide is a composite metaloxide having a composition in which a region including an oxideincluding gallium as a main component and a region includingIn_(X2)Zn_(Y2)O_(Z2) or InO_(X1) as a main component are mixed.Surrounding portions of the region including an oxide including galliumas a main component and the region including In_(X2)Zn_(Y2)O_(Z2) orInO_(X1) as a main component are unclear (blurred), so that boundariesare not clearly observed in some cases.

For example, in the conceptual view in FIG. 1 , the region 001corresponds to the region including an oxide including gallium as a maincomponent and the region 002 corresponds to the region includingIn_(X2)Zn_(Y2)O_(Z2) or InO_(X1) as a main component. The regionincluding an oxide including gallium as a main component and the regionincluding In_(X2)Zn_(Y2)O_(Z2) or InO_(X1) as a main component may eachbe referred to as a nanoparticle. The diameter of the nanoparticle isgreater than or equal to 0.5 nm and less than or equal to 10 nm,typically greater than or equal to 1 nm and less than or equal to 2 nm.Surrounding portions of the nanoparticles are unclear (blurred), so thata boundary is not clearly observed in some cases.

Note that the sizes of the region 001 and the region 002 can beevaluated with energy dispersive X-ray spectroscopy EDX mapping obtainedby EDX. For example, the diameter of the region 001 is observed to begreater than or equal to 0.5 nm and less than or equal to 10 nm, or lessthan or equal to 3 nm in the EDX mapping of a cross-sectional photographin some cases. The density of an element that is a main component isgradually lowered from the central portion of the region toward thesurrounding portion. For example, when the concentration of the element(hereinafter also referred to as abundance) in an EDX mapping graduallydecreases from the central portion toward the surrounding portion, thesurrounding portion of the region is indistinct (unclear (blurred)) inobservation of the EDX mapping of the cross-sectional photograph. Forexample, from the central portion toward the surrounding portion in theregion including InO_(X1) as a main component, the number of In atomsgradually reduces and the number of Zn atoms increases, so that theregion gradually changes into the region including In_(X2)Zn_(Y2)O_(Z2)as a main component. Thus, the surrounding portion of the regionincluding GaO_(X3) as a main component is indistinct in observation ofthe EDX mapping.

For this reason, when [In] in the region 001 or the region 002 includedin the In—Ga—Zn oxide is 1, [Ga] and [Zn] are not limited to integers.That is, since surrounding portions of the region 001 and the region 002are unclear and concentration distributions of the metal elements aregenerated in the region 001 and the region 002, [Ga] and [Zn] are notnecessarily integers when [In] is 1. Thus, even in the In—Ga—Zn oxideincluding the region 001 and the region 002, [Ga] and [Zn] are notlimited to integers when [In] is 1.

Here, in the case where an In-M-Zn oxide can be represented in the formof InM_(m)Zn_(n)O_(p), for example, the region 001 included in thecomposite oxide of one embodiment of the present invention can berepresented as InM_(m1)Zn_(n1)O_(p1). Similarly, the region 002 includedin the composite oxide of one embodiment of the present invention can berepresented as InM_(m2)Zn_(n2)O_(p2). Note that m, n, p, m1, n1, p1, m2,n2, and p2 described above are each an integer or a non-integer.

In this specification and the like, the In-M-Zn oxide represented asInM_(m)Zn_(n)O_(p), InM_(m1)Zn_(n1)O_(p1), or InM_(m2)Zn_(n2)O_(p2) isreferred to as InMZnO-based oxide in some cases. In the stoichiometricproportion of InMZnO-based oxide, when In is 1, each of M and Zn is aninteger or a non-integer. Note that the case where the value of thestoichiometric composition is varied between portions in the region isincluded.

A crystal structure of the In—Ga—Zn oxide with the CAC composition isnot particularly limited. The region 001 and the region 002 may havedifferent crystal structures.

Here, an In—Ga—Zn—O-based metal oxide is referred to as IGZO in somecases. IGZO is a commonly known name and sometimes refers to onecompound formed of In, Ga, Zn, and O.

A crystalline compound can be given as an example of theIn—Ga—Zn—O-based metal oxide. The crystalline compound has a singlecrystal structure, a polycrystalline structure, or a c-axis alignedcrystalline (CAAC) structure. Note that the CAAC structure is a layeredcrystal structure in which a plurality of IGZO nanocrystals have c-axisalignment and are connected in the a-b plane without alignment.

In contrast, of the CAC-OS in the In—Ga—Zn oxide, the crystal structureis a secondary element. In this specification, CAC-IGZO can be definedas a metal oxide including In, Ga, Zn, and O in the state where aplurality of regions including Ga as a main component and a plurality ofregions including In as a main component are each dispersed randomlyforming a mosaic pattern.

For example, in the conceptual view in FIG. 1 , the region 001corresponds to the region including Ga as a main component and theregion 002 corresponds to the region including In as a main component.The region including Ga as a main component and the region including Inas a main component may each be referred to as a nanoparticle. Thediameter of the nanoparticle is greater than or equal to 0.5 nm and lessthan or equal to 10 nm, typically less than or equal to 3 nm.Surrounding portions of the nanoparticles are unclear (blurred), so thata boundary is not clearly observed in some cases.

Note that the crystallinity of the CAC-OS in an In—Ga—Zn oxide can beanalyzed by electron diffraction. For example, a ring-like region withhigh luminance is observed in an electron diffraction pattern image.Furthermore, a plurality of spots are observed in the ring-shaped regionin some cases.

As described above, the CAC-OS in the In—Ga—Zn oxide has a structuredifferent from that of an IGZO compound in which metal elements areevenly distributed, and has properties different from those of the IGZOcompound. That is, in the CAC-OS in the In—Ga—Zn oxide, regionsincluding an oxide including gallium or the like as a main component andregions including In_(X2)Zn_(Y2)O_(Z2) or InO_(X1) as a main componentare separated from each other, and the regions including the respectiveelements as the main components form a mosaic pattern.

The region including In_(X2)Zn_(Y2)O_(Z2) or InO_(X1) as a maincomponent is a region whose conductivity is higher than that of theregion including an oxide including gallium or the like as a maincomponent. In other words, when carriers flow through the regionsincluding In_(X2)Zn_(Y2)O_(Z2) or InO_(X1) as a main component, theconductivity of an oxide semiconductor is exhibited. Accordingly, whenthe regions including In_(X2)Zn_(Y2)O_(Z2) or InO_(X1) as a maincomponent are distributed in an oxide semiconductor like a cloud, highfield-effect mobility (μ) can be achieved. Note that the regionincluding In_(X2)Zn_(Y2)O_(Z2) or InO_(X1) as a main component can besaid to be a semiconductor region whose properties are close to those ofa conductor.

In contrast, the region including an oxide including gallium or the likeas a main component is a region whose insulating property is higher thanthat of the region including In_(X2)Zn_(Y2)O_(Z2) or InO_(X1) as a maincomponent. In other words, when the regions including an oxide includinggallium or the like as a main component are distributed in an oxidesemiconductor, leakage current can be suppressed and favorable switchingoperation can be achieved. Note that the region includingIn_(a)Ga_(b)Zn_(c)O_(d) or the like as a main component can be said tobe a semiconductor region whose properties are close to those of aninsulator.

Accordingly, when the CAC-OS in the In—Ga—Zn oxide is used for asemiconductor element, the insulating property derived from the oxideincluding gallium or the like and the conductivity derived fromIn_(X2)Zn_(Y2)O_(Z2) or InO_(X1) complement each other, whereby highon-state current (I_(on)), high field-effect mobility (μ), and lowoff-state current (I_(off)) can be achieved.

A semiconductor element that includes a CAC-OS in an In—Ga—Zn oxide hashigh reliability. Thus, the CAC-OS in the In—Ga—Zn oxide is the mostsuitable for a variety of semiconductor devices typified by a display.

<Transistor Including Metal Oxide>

Next, the case where the metal oxide is used as a semiconductor in atransistor is described.

Note that with the use of the metal oxide as a semiconductor in atransistor, the transistor having high field-effect mobility and highswitching characteristics can be achieved. In addition, the transistorhaving high reliability can be achieved.

FIG. 2(A) is a schematic view of a transistor including the metal oxidein a channel region. The transistor in FIG. 2(A) includes a source, adrain, a first gate, a second gate, a first gate insulating portion(GI1), a second gate insulating portion (GI2), and a channel. Theresistance of the channel of the transistor can be controlled by apotential applied to the gate. That is, conduction (the on state of thetransistor) or non-conduction (the off state of the transistor) betweenthe source and the drain can be controlled by a potential applied to thefirst gate or the second gate.

The channel includes a CAC-OS in which the regions 001 having a firstband gap and the regions 002 having a second band gap are distributedlike a cloud. Note that the first band gap is larger than the secondband gap. Thus, in this specification, the first band gap is denoted aswide Eg, Eg001, or the like, in some cases. The second band gap isdenoted as narrow Eg, Eg002, or the like, in some cases.

For example, the case where the In—Ga—Zn oxide with the CAC compositionis used as the CAC-OS in the channel is described. The In—Ga—Zn oxidewith the CAC composition has a (cloud-like) composition in whichmaterials are separated into, as the region 001, a region includingIn_(a)Ga_(b)Zn_(c)O_(d) as a main component and having higher Gaconcentration than the region 002, and, as the region 002, a regionincluding In_(X2)Zn_(Y2)O_(Z2) or InO_(X1) as a main component andhaving higher In concentration than the region 001 and form a mosaicpattern, and In_(a)Ga_(b)Zn_(c)O_(d), and InO_(X1) orIn_(X2)Zn_(Y2)O_(Z2) are distributed in the film. Note that the region001 including In_(a)Ga_(b)Zn_(c)O_(d) as a main component has a band gaplarger than that of the region 002 including In_(X2)Zn_(Y2)O_(Z2) orInO_(X1) as a main component.

A conduction model of the transistor illustrated in FIG. 2(A), whichincludes the CAC-OS in the channel, is described. FIG. 2(B) is aschematic view showing distribution of energy levels between the sourceand the drain of the transistor illustrated in FIG. 2(A). FIG. 2(C) is aconduction band diagram on solid line X-X′ in the transistor illustratedin FIG. 2(A). Note that in each conduction band diagram, a solid lineindicates the energy of the conduction band minimum. A dashed-dottedline represented by E_(f) indicates the energy of the quasi-Fermi levelof electrons. Here, a negative voltage is applied between the gate andthe source as a first gate voltage and a drain voltage (V_(d)>0) isapplied between the source and the drain.

When a negative gate voltage is applied to the transistor illustrated inFIG. 2(A), an energy of a conduction band minimum CB₀₀₁ derived from theregion 001 and an energy of a conduction band minimum CB₀₀₂ derived fromthe region 002 are formed between the source and the drain asillustrated in FIG. 2(B). Since the first band gap is larger than thesecond band gap, the potential barrier of the energy of the conductionband minimum CB₀₀₁ is higher than the potential barrier of the energy ofthe conduction band minimum CB₀₀₂. That is, the maximum value of thepotential barrier in the channel is a value derived from the region 001.Thus, the use of the CAC-OS in the channel can suppress leakage currentand achieve a transistor having high switching characteristics.

As illustrated in FIG. 2(C), the band gap of the region 001 having thefirst band gap is relatively wider than the band gap of the region 002having the second band gap; thus, the energy level of the conductiveband minimum (the Ec edge) derived from the region 001 having the firstband gap can exist at a relatively higher level than the energy level ofthe conductive band minimum (the Ec edge) derived from the region 002having the second band gap.

For example, it is assumed that a component of the region 001 having thefirst band gap is an In—Ga—Zn oxide (In:Ga:Zn=1:1:1 [atomic ratio]), anda component of the region 002 having the second band gap is an In—Znoxide (In:Zn=2:3 [atomic ratio]). In this case, the first band gap is3.3 eV or a value in the vicinity thereof, and the second band gap is2.4 eV or a value in the vicinity thereof. Note that values obtained bymeasurement of single films of respective materials with an ellipsometerare used as the values of the band gaps.

In the above assumption, the difference between the first band gap andthe second band gap is 0.9 eV. In one embodiment of the presentinvention, the difference between the first band gap and the second bandgap is at least 0.1 eV or more. Note that the level of the valence bandmaximum derived from the region 001 having the first band gap isdifferent from the level of the valence band maximum derived from theregion 002 having the second band gap in some cases; thus, thedifference between the first band gap and the second band gap ispreferably 0.3 eV or more, further preferably 0.4 eV or more.

In the above assumption, carriers flow through the CAC-OS owing to anIn—Zn oxide which has the second band gap, i.e., a narrow band gap. Atthis time, the carriers overflow from the second band gap into theIn—Ga—Zn oxide side which has the first band gap, i.e., a wide band gap.In other words, carriers are more easily generated in an In—Zn oxidewhich has a narrow band gap, and the carriers move to an In—Ga—Zn oxidewhich has a wide band gap.

Note that in the metal oxide where the channel is formed, the regions001 and the regions 002 form a mosaic pattern and the regions 001 andthe regions 002 are irregularly unevenly distributed. For this reason,the conduction band diagram on solid line X-X′ is merely an example.

It is basically acceptable as long as a band in which the region 002 isbetween the regions 001 is formed as shown in FIG. 3(A). Alternatively,it is acceptable as long as a band in which the region 001 is betweenthe regions 002 is formed.

In a connection portion of the region 001 having the first band gap andthe region 002 having the second band gap in the actual CAC-OS, anaggregation state and the composition of the regions probably becomeunstable. Accordingly, as illustrated in FIG. 3(B) and FIG. 3(C), thebands change not discontinuously but continuously in some cases. Inother words, the first band gap and the second band gap work togetherwhen carriers flow through the CAC-OS.

FIG. 4 shows a model of a schematic band diagram of the transistor inthe direction along X-X′ in FIG. 2(A), which corresponds to theschematic view in FIG. 2(B). Note that when a voltage is applied to thefirst gate, the same voltage is simultaneously applied to the secondgate. FIG. 4(A) shows a state (ON State) in which, as a first gatevoltage V_(g), a positive voltage (V_(g)>0) is applied between each ofthe gates and the source. FIG. 4(B) shows a state in which the firstgate voltage V_(g) is not applied (V_(g)=0). FIG. 4(C) shows a state(OFF State) in which, as the first gate voltage V_(g), a negativevoltage (V_(g)<0) is applied between each of the gates and the source.Note that in the channel, a dashed line indicates the energy of theconduction band minimum in the case where no voltage is applied, and asolid line indicates the energy of the conduction band minimum in thecase where a voltage is applied. A dashed-dotted line represented byE_(f) indicates the energy of the quasi-Fermi level of electrons.

In a transistor including the CAC-OS in a channel, the region 001 havingthe first band gap and the region 002 having the second band gapelectrically interact with each other. In other words, the region 001having the first band gap and the region 002 having the second band gapfunction complementarily.

In other words, in the case where a forward voltage is applied as shownin FIG. 4(A), the conduction band of the region 001 becomes lower thanthe conduction band of the region 002. Accordingly, carriers flow in notonly the conduction band of the region 002 but also the conduction bandof the region 001, so that a high on-state current can be obtained.Meanwhile, in the case where a reverse voltage is applied as shown inFIG. 4(B) and FIG. 4(C), the conduction bands of the region 001 and theregion 002 become higher, which probably causes a significant reductionin the current flowing between the source and the drain.

FIG. 5 shows a model of a schematic band diagram of the transistor onsolid line X-X′ in FIG. 2(A), which corresponds to the schematic view inFIG. 2(C). Note that when a voltage is applied to the first gate, thesame voltage is simultaneously applied to the second gate. FIG. 5(A)shows a state (ON State) in which, as the first gate voltage V_(g), apositive voltage (V_(g)>0) is applied between each of the gates and thesource. FIG. 5(B) shows a state in which the first gate voltage V_(g) isnot applied (V_(g)=0). FIG. 5(C) shows a state (OFF State) in which, asthe first gate voltage V_(g), a negative voltage (V_(g)<0) is appliedbetween each of the gates and the source. Note that in the channel, asolid line indicates the energy of the conduction band minimum. Thedashed-dotted line represented by E_(f) indicates the energy of thequasi-Fermi level of electrons. Here, the energy difference between theconduction band minimum of the region 001 and the conduction bandminimum of the region 002 is represented as ΔEc. Furthermore, ΔEc(V_(g)=0) indicates ΔEc in a state where a voltage is not applied(V_(g)=0), ΔEc (V_(g)>0) indicates ΔEc in a state where a voltage atwhich the transistor is turned on (V_(g)>0) is applied, and ΔEc(V_(g)<0) indicates ΔEc in a state where a negative voltage (V_(g)<0) isapplied.

As illustrated in FIG. 5(A), when a potential at which the transistor isturned on (V_(g)>0) is applied to the first gate, ΔEc (V_(g)>0)<ΔEc(V_(g)=0) is satisfied. Thus, electrons flow in the region 002 havingthe second band gap with the low energy level of the conductive bandminimum (the Ec edge) and serving as a main conduction path; at the sametime, electrons also flow in the region 001 having the first band gap.Therefore, high current drive capability in the on state of thetransistor, i.e., high on-state current and high field-effect mobilitycan be obtained.

In contrast, as illustrated in FIG. 5(B) and FIG. 5(C), when a voltagelower than the threshold voltage (V_(g)≤0) is applied to the first gate,the region 001 having the first band gap serves as a dielectric(insulator), so that the conduction path in the region 001 is blocked.The region 002 having the second band gap is in contact with the region001 having the first band gap. Consequently, the region 001 having thefirst band gap electrically interacts with itself and also with theregion 002 having the second band gap, and thus, even the conductionpath in the region 002 having the second band gap is blocked.Accordingly, the whole channel is brought into a non-conductive state,and the transistor is turned off. Therefore, ΔEc (V_(g)=0)<ΔEc (V_(g)<0)is satisfied.

As described above, with the use of the CAC-OS in a transistor, it ispossible to reduce or prevent leakage current between a gate and asource or a drain, which is generated when the transistor operates, forexample, when a potential difference is generated between the gate andthe source or the drain.

A semiconductor with a low carrier density is preferably used in atransistor. A highly purified intrinsic or substantially highly purifiedintrinsic metal oxide has few carrier generation sources and thus canhave a low carrier density. The highly purified intrinsic orsubstantially highly purified intrinsic metal oxide has a low density ofdefect states and accordingly has a low density of trap states in somecases.

Charge trapped by the trap states in the metal oxide takes a long timeto be released and may behave like fixed charge. Thus, a transistorwhose channel region is formed in a metal oxide having a high density oftrap states has unstable electrical characteristics in some cases.

Accordingly, in order to obtain stable electrical characteristics of thetransistor, it is effective to reduce the concentration of impurities inthe metal oxide. In addition, in order to reduce the concentration ofimpurities in the metal oxide, the concentration of impurities in anadjacent film is also preferably reduced. Examples of impurities includehydrogen, alkali metal, alkaline earth metal, iron, nickel, and silicon.

Here, the influence of each impurity in the metal oxide will bedescribed.

When silicon or carbon that is a Group 14 element is contained in themetal oxide, defect states are formed in the metal oxide. Thus, theconcentration of silicon or carbon in the metal oxide and theconcentration of silicon or carbon around an interface with the metaloxide (the concentration measured by secondary ion mass spectrometrySIMS) is set to be lower than or equal to 2×10¹⁸ atoms/cm³, preferablylower than or equal to 2×10¹⁷ atoms/cm³.

When the metal oxide contains an alkali metal or an alkaline earthmetal, defect states are formed and carriers are generated, in somecases. Thus, a transistor including a metal oxide that contains analkali metal or an alkaline earth metal is likely to be normally on.Therefore, it is preferable to reduce the concentration of an alkalimetal or an alkaline earth metal in the metal oxide. Specifically, theconcentration of an alkali metal or an alkaline earth metal in the metaloxide measured by SIMS is set to be lower than or equal to 1×10¹⁸atoms/cm³, preferably lower than or equal to 2×10¹⁶ atoms/cm³.

Hydrogen included in the metal oxide reacts with oxygen bonded to ametal atom to be water, and thus causes an oxygen vacancy (Vo) in somecases. Due to entry of hydrogen into the oxygen vacancy (Vo), anelectron serving as a carrier is generated in some cases. Furthermore,in some cases, bonding of part of hydrogen to oxygen bonded to a metalatom generates an electron serving as a carrier. Thus, a transistorincluding the metal oxide that includes hydrogen is likely to benormally on. Accordingly, hydrogen in the metal oxide is preferablyreduced as much as possible. Specifically, the hydrogen concentration ofthe metal oxide, which is measured by SIMS, is set to be lower than1×10²⁰ atoms/cm³, preferably lower than 1×10¹⁹ atoms/cm³, furtherpreferably lower than 5×10¹⁸ atoms/cm³, still further preferably lowerthan 1×10¹⁸ atoms/cm³.

Note that the oxygen vacancies (Vo) in the metal oxide can be reduced byintroduction of oxygen into the metal oxide. That is, the oxygenvacancies (Vo) in the metal oxide disappear when the oxygen vacancies(Vo) are filled with oxygen. Accordingly, diffusion of oxygen in themetal oxide can reduce the oxygen vacancies (Vo) in a transistor andimprove the reliability.

Note that as a method for introducing oxygen into the metal oxide, forexample, an oxide in which oxygen content is higher than the oxygencontent in the stoichiometric composition can be provided in contactwith the metal oxide. That is, in the oxide, a region including oxygenin excess of that in the stoichiometric composition (hereinafter alsoreferred to as an excess oxygen region) is preferably formed. Inparticular, in the case of using a metal oxide in a transistor, an oxideincluding an excess oxygen region is provided in a base film, aninterlayer film, or the like in the vicinity of the transistor, wherebyoxygen vacancies in the transistor are reduced, and the reliability canbe improved.

When a metal oxide in which impurities are sufficiently reduced is usedfor a channel formation region in a transistor, stable electricalcharacteristics can be obtained.

<Method for Forming Metal Oxide Film>

An example of a method for forming the metal oxide film is describedbelow.

The metal oxide film is preferably formed at a temperature higher thanor equal to room temperature and lower than 140° C. Note that roomtemperature includes not only the case where temperature control is notperformed but also the case where temperature control is performed,e.g., the case where a substrate is cooled.

As a sputtering gas, a rare gas (typically argon), oxygen, or a mixedgas of a rare gas and oxygen is used as appropriate. In the case of themixed gas, the proportion of the oxygen gas in the whole film formationgas is higher than or equal to 0% and lower than or equal to 30%,preferably higher than or equal to 5% and lower than or equal to 20%.

Note that when the sputtering gas contains oxygen, oxygen can be addedto a film under the metal oxide and an excess oxygen region can beprovided at the same time as the formation of the metal oxide film. Inaddition, increasing the purity of a sputtering gas is necessary. Forexample, as an oxygen gas or an argon gas used for a sputtering gas, agas highly purified to have a dew point of −40° C. or lower, preferably−80° C. or lower, further preferably −100° C. or lower, still furtherpreferably −120° C. or lower is used, whereby entry of moisture or thelike into the metal oxide can be prevented as much as possible.

In the case where the metal oxide film is formed by a sputtering method,a chamber in a sputtering apparatus is preferably evacuated to a highvacuum (to the degree of approximately 5×10⁻⁷ Pa to 1×10⁻⁴ Pa) with anadsorption vacuum pump such as a cryopump in order to remove as muchwater as possible or the like, which serves as an impurity for the metaloxide. Alternatively, a turbo molecular pump and a cold trap arepreferably combined so as to prevent a backflow of a gas, especially agas containing carbon or hydrogen from an exhaust system to the insideof the chamber.

As a target, an In—Ga—Zn metal oxide target can be used. For example, ametal oxide target having [In]:[Ga]:[Zn]=4:2:4.1 [atomic ratio],[In]:[Ga]:[Zn]=5:1:7 [atomic ratio], or the atomic ratio in theneighborhood thereof is preferably used.

In the sputtering apparatus, the target may be rotated or moved. Forexample, the magnet unit is oscillated vertically and/or horizontallyduring the film formation, whereby the composite metal oxide of thepresent invention can be formed. For example, the target may be rotatedor oscillated with a beat (also referred to as rhythm, beat, pulse,frequency, period, cycle, or the like) of greater than or equal to 0.1Hz and less than or equal to 1 kHz. Alternatively, the magnet unit maybe oscillated with a beat of greater than or equal to 0.1 Hz and lessthan or equal to 1 kHz.

The metal oxide of the present invention can be formed, for example, byusing a mixed gas of oxygen and a rare gas in which the proportion ofoxygen is approximately 10% as a sputtering gas; setting the substratetemperature to 130° C.; and oscillating an In—Ga—Zn metal oxide targethaving [In]:[Ga]:[Zn]=4:2:4.1 [atomic ratio] during the film formation.

The structure described in this embodiment can be used in combinationwith any of the structures described in the other embodiments or theother examples as appropriate.

Embodiment 2

In this embodiment, semiconductor devices of one embodiment of thepresent invention, and manufacturing methods thereof will be describedwith reference to FIG. 6 to FIG. 15 .

2-1. Structure Example 1 of Semiconductor Device

FIG. 6(A) is a top view of a transistor 100 that is a semiconductordevice of one embodiment of the present invention; FIG. 6(B) correspondsto a cross-sectional view of a cross section taken along dashed-dottedline X1-X2 in FIG. 6(A); and FIG. 6(C) corresponds to a cross-sectionalview of a cross section taken along dashed-dotted line Y1-Y2 in FIG.6(A). Note that in FIG. 6(A), some components of the transistor 100(e.g., an insulating film functioning as a gate insulating film) are notillustrated to avoid complexity. The direction of the dashed-dotted lineX1-X2 may be called a channel length direction, and the direction of thedashed-dotted line Y1-Y2 may be called a channel width direction. Notethat as in FIG. 6(A), some components are not illustrated in some casesin top views of transistors in the following drawings.

The transistor 100 illustrated in FIGS. 6(A), 6(B), and 6(C) is what iscalled a top-gate transistor.

The transistor 100 includes an insulating film 104 over a substrate 102,a metal oxide 108 over the insulating film 104, an insulating film 110over the metal oxide 108, a conductive film 112 over the insulating film110, and an insulating film 116 over the insulating film 104, the metaloxide 108, and the conductive film 112.

The metal oxide 108 includes a region overlapping with the conductivefilm 112 with the insulating film 110 interposed therebetween. Forexample, the metal oxide 108 preferably contains In, M (M is Al, Ga, Y,or Sn), and Zn.

The metal oxide 108 includes regions 108 n in regions which do notoverlap with the conductive film 112 and are in contact with theinsulating film 116. The regions 108 n are n-type regions in the metaloxide 108 described above. Note that the regions 108 n are in contactwith the insulating film 116, and the insulating film 116 containsnitrogen or hydrogen. Accordingly, nitrogen or hydrogen in theinsulating film 116 is added to the regions 108 n to increase thecarrier density, thereby making the regions 108 n n-type.

The metal oxide 108 preferably includes a region in which the atomicproportion of In is larger than the atomic proportion of M. For example,the atomic ratio of In to M and Zn in the metal oxide 108 is preferablyIn:M:Zn=4:2:3 or in the neighborhood thereof.

Note that the composition of the metal oxide 108 is not limited to theabove. For example, the atomic ratio of In to M and Zn in the metaloxide 108 may be In:M:Zn=5:1:6 or in the neighborhood thereof. The term“neighborhood” includes the following: when In is 5, M is greater thanor equal to 0.5 and less than or equal to 1.5, and Zn is greater than orequal to 5 and less than or equal to 7.

When the metal oxide 108 has a region in which the atomic proportion ofIn is larger than the atomic proportion of M, the transistor 100 canhave high field-effect mobility. Specifically, the field-effect mobilityof the transistor 100 can exceed 10 cm²/Vs, preferably exceed 30 cm²/Vs.

For example, with the use of the transistor with high field-effectmobility in a gate driver that generates a gate signal, the displaydevice with a small frame width (also referred to as a narrow frame) canbe provided. Furthermore, with the use of the above transistor with highfield-effect mobility in a source driver included in a display device(particularly a demultiplexer connected to an output terminal of a shiftregister included in the source driver), a display device to which fewerwirings are connected can be provided.

Meanwhile, even when the metal oxide 108 includes a region in which theatomic proportion of In is larger than the atomic proportion of M, thefield-effect mobility might be low if the metal oxide 108 has highcrystallinity.

Note that the crystallinity of the metal oxide 108 can be determined byanalysis by XRD (X-Ray Diffraction) or with a transmission electronmicroscope (TEM), for example.

First, oxygen vacancies that might be formed in the metal oxide 108 willbe described.

Oxygen vacancies formed in the metal oxide 108 adversely affect thetransistor characteristics and therefore cause a problem. For example,when oxygen vacancies are formed in the metal oxide 108, hydrogen isbonded to the oxygen vacancies to serve as a carrier supply source. Thecarrier supply source generated in the metal oxide 108 causes a changein the electrical characteristics, typically, a shift in the thresholdvoltage, of the transistor 100 including the metal oxide 108. Therefore,it is preferable that the amount of oxygen vacancies in the metal oxide108 be as small as possible.

In view of the above, one embodiment of the present invention employs astructure in which the insulating film in the vicinity of the metaloxide 108, specifically, one or both of the insulating film 110 which isformed over the metal oxide 108 and the insulating film 104 which isformed below the metal oxide 108 contains excess oxygen. Oxygen orexcess oxygen is transferred from one or both of the insulating film 104and the insulating film 110 to the metal oxide 108, whereby oxygenvacancies in the metal oxide can be reduced.

Impurities such as hydrogen and moisture entering the metal oxide 108adversely affect the transistor characteristics and therefore cause aproblem. Thus, it is preferable that the amount of impurities such ashydrogen and moisture in the metal oxide 108 be as small as possible.

Note that it is preferable to use, as the metal oxide 108, a metal oxidein which the impurity concentration is low and the density of defectstates is low, in which case the transistor having excellent electricalcharacteristics can be fabricated. Here, the state in which the impurityconcentration is low and the density of defect states is low (the amountof oxygen vacancies is small) is referred to as highly purifiedintrinsic or substantially highly purified intrinsic. A highly purifiedintrinsic or substantially highly purified intrinsic metal oxide has fewcarrier generation sources, and thus can have a low carrier density.Thus, a transistor in which a channel region is formed in the metaloxide rarely has electrical characteristics with a negative thresholdvoltage (also referred to as normally-on). A highly purified intrinsicor substantially highly purified intrinsic metal oxide has a low densityof defect states and accordingly has a low density of trap states insome cases. Furthermore, the highly purified intrinsic or substantiallyhighly purified intrinsic metal oxide has an extremely low off-statecurrent; thus, even an element having a channel width of 1×10⁶ μm and achannel length of 10 μm can have characteristics in which the off-statecurrent is less than or equal to the measurement limit of asemiconductor parameter analyzer, that is, less than or equal to 1×10⁻¹³A, at a voltage between a source electrode and a drain electrode (drainvoltage) of 1 V to 10 V.

As illustrated in FIGS. 6(A), 6(B), and 6(C), the transistor 100 mayfurther include an insulating film 118 over the insulating film 116, aconductive film 120 a electrically connected to the region 108 n throughan opening 141 a formed in the insulating films 116 and 118; and aconductive film 120 b electrically connected to the region 108 n throughan opening 141 b formed in the insulating films 116 and 118.

Note that in this specification and the like, the insulating film 104may be referred to as a first insulating film, the insulating film 110may be referred to as a second insulating film, the insulating film 116may be referred to as a third insulating film, and the insulating film118 may be referred to as a fourth insulating film. The conductive film112, the conductive film 120 a, and the conductive film 120 b functionas a gate electrode, a source electrode, and a drain electrode,respectively.

The insulating film 110 functions as a gate insulating film. Theinsulating film 110 includes an excess oxygen region. Since theinsulating film 110 includes the excess oxygen region, excess oxygen canbe supplied to the metal oxide 108. As a result, oxygen vacancies thatmight be formed in the metal oxide 108 can be filled with excess oxygen,and the semiconductor device having high reliability can be provided.

Note that to supply excess oxygen to the metal oxide 108, excess oxygenmay be supplied to the insulating film 104 that is formed below themetal oxide 108. In that case, excess oxygen contained in the insulatingfilm 104 might also be supplied to the regions 108 n. It is notdesirable that excess oxygen be supplied to the regions 108 n becausethe resistance of the regions 108 n is increased. In contrast, in thestructure in which the insulating film 110 formed over the metal oxide108 contains excess oxygen, excess oxygen can be selectively suppliedonly to a region overlapping with the conductive film 112.

2-2. Components of Semiconductor Device

Next, components of the semiconductor device of this embodiment will bedescribed in detail.

[Substrate]

Although there is no particular limitation on a material and the like ofthe substrate 102, the material needs to have heat resistance at leasthigh enough to withstand heat treatment to be performed later. Forexample, a glass substrate, a ceramic substrate, a quartz substrate, asapphire substrate, or the like may be used as the substrate 102.Alternatively, a single crystal semiconductor substrate or apolycrystalline semiconductor substrate made of silicon or siliconcarbide, a compound semiconductor substrate made of silicon germanium orthe like, an SOI substrate, or the like can be used, or any of thesesubstrates provided with a semiconductor element may be used as thesubstrate 102. Note that in the case where a glass substrate is used asthe substrate 102, a large-sized substrate having any of the followingsizes is used: the 6th generation (1500 mm×1850 mm), the 7th generation(1870 mm×2200 mm), the 8th generation (2200 mm×2400 mm), the 9thgeneration (2400 mm×2800 mm), and the 10th generation (2950 mm×3400 mm);thus, a large-sized display device can be fabricated.

Alternatively, a flexible substrate may be used as the substrate 102,and the transistor 100 may be formed directly on the flexible substrate.Alternatively, a separation layer may be provided between the substrate102 and the transistor 100. The separation layer can be used when partor the whole of a semiconductor device completed thereover is separatedfrom the substrate 102 and transferred onto another substrate. In such acase, the transistor 100 can be transferred onto a substrate having lowheat resistance or a flexible substrate as well.

[First Insulating Film]

The insulating film 104 can be formed by a sputtering method, a CVDmethod, an evaporation method, a pulsed laser deposition (PLD) method, aprinting method, a coating method, or the like as appropriate. Forexample, the insulating film 104 can be formed to have a single layer ora stacked layer including an oxide insulating film or a nitrideinsulating film. To improve the properties of the interface with themetal oxide 108, at least a region of the insulating film 104 which isin contact with the metal oxide 108 is preferably formed using an oxideinsulating film. When the insulating film 104 is formed using an oxideinsulating film from which oxygen is released by heating, oxygencontained in the insulating film 104 can be moved to the metal oxide 108by heat treatment.

The thickness of the insulating film 104 can be greater than or equal to50 nm, greater than or equal to 100 nm and less than or equal to 3000nm, or greater than or equal to 200 nm and less than or equal to 1000nm. By increasing the thickness of the insulating film 104, the amountof oxygen released from the insulating film 104 can be increased;furthermore, interface states at the interface between the insulatingfilm 104 and the metal oxide 108 and oxygen vacancies included in themetal oxide 108 can be reduced.

For example, the insulating film 104 can be formed to have a singlelayer or a stacked layer using silicon oxide, silicon oxynitride,silicon nitride oxide, silicon nitride, aluminum oxide, hafnium oxide,gallium oxide, a Ga—Zn oxide, or the like. In this embodiment, theinsulating film 104 has a stacked-layer structure of a silicon nitridefilm and a silicon oxynitride film. With the insulating film 104 havingsuch a stacked-layer structure using a silicon nitride film on a lowerlayer side and a silicon oxynitride film on an upper layer side, oxygencan be efficiently introduced into the metal oxide 108.

[Conductive Film]

The conductive film 112 functioning as a gate electrode, the conductivefilm 120 a functioning as a source electrode, and the conductive film120 b functioning as a drain electrode can each be formed using a metalelement selected from chromium (Cr), copper (Cu), aluminum (Al), gold(Au), silver (Ag), zinc (Zn), molybdenum (Mo), tantalum (Ta), titanium(Ti), tungsten (W), manganese (Mn), nickel (Ni), iron (Fe), and cobalt(Co); an alloy including these metal elements as its component; an alloyincluding a combination of these metal elements; or the like.

Furthermore, the conductive films 112, 120 a, and 120 b can be formedusing an oxide conductor or a metal oxide, such as an oxide includingindium and tin (In—Sn oxide), an oxide including indium and tungsten(In—W oxide), an oxide including indium, tungsten, and zinc (In—W—Znoxide), an oxide including indium and titanium (In—Ti oxide), an oxideincluding indium, titanium, and tin (In—Ti—Sn oxide), an oxide includingindium and zinc (In—Zn oxide), an oxide including indium, tin, andsilicon (In—Sn—Si oxide), or an oxide including indium, gallium, andzinc (In—Ga—Zn oxide).

Here, an oxide conductor is described. In this specification and thelike, an oxide conductor may be referred to as OC (Oxide Conductor). Forexample, oxygen vacancies are formed in a metal oxide, and then hydrogenis added to the oxygen vacancies, so that a donor level is formed in thevicinity of the conduction band. This increases the conductivity of themetal oxide; accordingly, the metal oxide becomes a conductor. The metaloxide having become a conductor can be referred to as an oxideconductor. Metal oxides generally have a visible light transmittingproperty because of their large energy gap. Meanwhile, an oxideconductor is a metal oxide having a donor level in the vicinity of theconduction band. Therefore, the influence of absorption due to the donorlevel is small in an oxide conductor, and an oxide conductor has avisible light transmitting property comparable to that of a metal oxide.

It is particularly preferred to use the oxide conductor described abovefor the conductive film 112, in which case excess oxygen can be added tothe insulating film 110.

A Cu—X alloy film (X is Mn, Ni, Cr, Fe, Co, Mo, Ta, or Ti) may be usedas the conductive films 112, 120 a, and 120 b. The use of a Cu—X alloyfilm enables fabrication costs to be reduced because processing can beperformed by a wet etching process.

Among the above-mentioned metal elements, it is particularly preferablethat any one or more selected from titanium, tungsten, tantalum, andmolybdenum be included in the conductive films 112, 120 a, and 120 b. Itis particularly preferable that a tantalum nitride film be used as eachof the conductive films 112, 120 a, and 120 b. The tantalum nitride filmhas conductivity and a high barrier property against copper or hydrogen.Furthermore, since a tantalum nitride film releases little hydrogen fromitself, it can be favorably used as the conductive film in contact withthe metal oxide 108 or the conductive film in the vicinity of the metaloxide 108.

The conductive films 112, 120 a, and 120 b can be formed by electrolessplating. As a material that can be deposited by electroless plating, forexample, any one or more selected from Cu, Ni, Al, Au, Sn, Co, Ag, andPd can be used. It is particularly favorable to use Cu or Ag because theresistance of the conductive film can be reduced.

[Second Insulating Film]

As the insulating film 110 functioning as a gate insulating film of thetransistor 100, an insulating layer including one or more of thefollowing films formed by a plasma enhanced chemical vapor deposition(PECVD) method, a sputtering method, or the like can be used: a siliconoxide film, a silicon oxynitride film, a silicon nitride oxide film, asilicon nitride film, an aluminum oxide film, a hafnium oxide film, anyttrium oxide film, a zirconium oxide film, a gallium oxide film, atantalum oxide film, a magnesium oxide film, a lanthanum oxide film, acerium oxide film, and a neodymium oxide film. Note that the insulatingfilm 110 may have a stacked-layer structure of two layers or astacked-layer structure of three or more layers.

The insulating film 110 that is in contact with the metal oxide 108functioning as a channel region of the transistor 100 is preferably anoxide insulating film and preferably includes a region including oxygenin excess of that in the stoichiometric composition (excess oxygenregion). In other words, the insulating film 110 is an insulating filmcapable of releasing oxygen. Note that in order to provide the excessoxygen region in the insulating film 110, the insulating film 110 isformed in an oxygen atmosphere, or the deposited insulating film 110 issubjected to heat treatment in an oxygen atmosphere, for example.

In the case of using hafnium oxide for the insulating film 110, thefollowing effects are attained. Hafnium oxide has a higher dielectricconstant than silicon oxide and silicon oxynitride. Therefore, thethickness of the insulating film 110 can be made large as compared withthe case of using silicon oxide; thus, leakage current due to tunnelcurrent can be low. That is, it is possible to achieve a transistor witha low off-state current. Moreover, hafnium oxide having a crystalstructure has a higher dielectric constant than hafnium oxide having anamorphous structure. Therefore, it is preferable to use hafnium oxidehaving a crystal structure, in order to obtain a transistor with a lowoff-state current. Examples of the crystal structure include amonoclinic crystal structure and a cubic crystal structure. Note thatone embodiment of the present invention is not limited to these.

It is preferable that the insulating film 110 have few defects andtypically have as few signals observed by electron spin resonance (ESR)spectroscopy as possible. Examples of the signals include an E′ centerobserved at a g-factor of 2.001. Note that the E′ center is due to thedangling bond of silicon. As the insulating film 110, a silicon oxidefilm or a silicon oxynitride film whose spin density due to the E′center is lower than or equal to 3×10¹⁷ spins/cm³ and preferably lowerthan or equal to 5×10¹⁶ spins/cm³ may be used.

[Metal Oxide]

As the metal oxide 108, the metal oxide described above can be used.

<Atomic Ratio>

Preferred ranges of the atomic ratio of indium, the element M, and zinccontained in the metal oxide according to the present invention aredescribed below with reference to FIG. 16(A), FIG. 16(B), and FIG.16(C). Note that the proportion of oxygen atoms is not illustrated inFIG. 16(A), FIG. 16(B), and FIG. 16(C). The terms of the atomic ratio ofindium, the element M, and zinc contained in the metal oxide are denotedby [In], [M], and [Zn], respectively.

In FIG. 16(A), FIG. 16(B), and FIG. 16(C), dashed lines indicate a linewhere the atomic ratio of [In]:[M]:[Zn]=(1+α):(1−α):1 (−1≤α≤1), a linewhere the atomic ratio of [In]:[M]; [Zn]=(1+α):(1−α):2, a line where theatomic ratio of [In]:[M]:[Zn]=(1+α):(1−α):3, a line where the atomicratio of [In]:[M]:[Zn]=(1+α):(1−α):4, and a line where the atomic ratioof [In]:[M]; [Zn]=(1+α):(1−α):5.

Dashed-dotted lines indicate a line representing the atomic ratio of[In]:[M]:[Zn]=5:1:β (β≥0), a line where the atomic ratio of[In]:[M]:[Zn]=2:1:β, a line where the atomic ratio of[In]:[M]:[Zn]=1:1:β, a line where the atomic ratio of[In]:[M]:[Zn]=1:2:β, a line where the atomic ratio of[In]:[M]:[Zn]=1:3:3, and a line where the atomic ratio of[In]:[M]:[Zn]=1:4:β.

A metal oxide having the atomic ratio of [In]:[M]:[Zn]=0:2:1 or a valuein the neighborhood thereof in FIG. 16(A), FIG. 16(B), and FIG. 16(C)tends to have a spinel crystal structure.

A plurality of phases coexist in the metal oxide in some cases(two-phase coexistence, three-phase coexistence, or the like). Forexample, in the case where the atomic ratio is in the neighborhood of[In]:[M]:[Zn]=0:2:1, two phases of a spinel crystal structure and alayered crystal structure are likely to coexist. In addition, in thecase where the atomic ratio is in the neighborhood of[In]:[M]:[Zn]=1:0:0, two phases of a bixbyite crystal structure and alayered crystal structure are likely to coexist. In the case where aplurality of phases coexist in the metal oxide, a grain boundary mightbe formed between different crystal structures.

A region A in FIG. 16(A) shows an example of the preferred ranges of theatomic ratio of indium to the element M and zinc contained in a metaloxide.

When the indium content of the metal oxide is increased, the carriermobility (electron mobility) of the metal oxide can be increased. Thus,a metal oxide having a high content of indium has higher carriermobility than a metal oxide having a low content of indium.

In contrast, when the indium content and the zinc content of a metaloxide become lower, carrier mobility becomes lower. Thus, in the case ofan atomic ratio of [In]:[M]:[Zn]=0:1:0 and a value in the neighborhoodthereof (e.g., a region C in FIG. 16(C)), insulation performance becomesbetter.

Accordingly, the metal oxide of one embodiment of the present inventionpreferably has an atomic ratio represented by the region A in FIG.16(A), with which high carrier mobility is obtained.

In the region A, particularly in a region B in FIG. 16(B), an excellentmetal oxide having high carrier mobility and high reliability can beobtained.

Note that the region B has an atomic ratio of [In]:[M]:[Zn]=4:2:3 to 4.1and values in the neighborhood thereof. The neighborhood includes anatomic ratio of [In]:[M]:[Zn]=5:3:4, for example. Note that the region Bhas an atomic ratio of [In]:[M]:[Zn]=5:1:6 and values in theneighborhood thereof, and an atomic ratio of [In]:[M]:[Zn]=5:1:7 andvalues in the neighborhood thereof.

Note that the property of a metal oxide is not uniquely determined by anatomic ratio. Even with the same atomic ratio, the property of a metaloxide might be different depending on a formation condition. Forexample, in the case where the metal oxide film is formed with asputtering apparatus, a film having an atomic ratio deviated from theatomic ratio of a target is formed. Furthermore, [Zn] in the film mightbe smaller than [Zn] in the target depending on the substratetemperature in film formation. Thus, the illustrated regions are each aregion representing an atomic ratio with which a metal oxide tends tohave specific characteristics, and boundaries of the region A to theregion C are not clear.

In the case where the metal oxide 108 is an In-M-Zn oxide, it ispreferable to use a target including polycrystalline In-M-Zn oxide asthe sputtering target. Note that the atomic ratio of the formed metaloxide 108 varies from the above atomic ratios of metal elements includedin the sputtering targets in a range of ±40%. For example, when asputtering target used for the metal oxide 108 has a composition ofIn:Ga:Zn=4:2:4.1 [atomic ratio], the composition of the formed metaloxide 108 may be In:Ga:Zn=4:2:3 [atomic ratio] or in the neighborhoodthereof. When a sputtering target used for the metal oxide 108 has acomposition of In:Ga:Zn=5:1:7 [atomic ratio], the composition of theformed metal oxide 108 may be 5:1:6 [atomic ratio] or in theneighborhood thereof.

The energy gap of the metal oxide 108 is 2 eV or more, preferably 2.5 eVor more. With the use of a metal oxide having such a wide energy gap,the off-state current of the transistor 100 can be reduced.

Furthermore, the metal oxide 108 preferably has a non-single-crystalstructure. Examples of the non-single-crystal structure include aCAAC-OS which will be described later, a polycrystalline structure, amicrocrystalline structure, and an amorphous structure. Among thenon-single-crystal structures, an amorphous structure has the highestdensity of defect states.

[Third Insulating Film]

The insulating film 116 contains nitrogen or hydrogen. A nitrideinsulating film can be given as the insulating film 116, for example.The nitride insulating film can be formed using silicon nitride, siliconnitride oxide, silicon oxynitride, or the like. The hydrogenconcentration in the insulating film 116 is preferably higher than orequal to 1×10²² atoms/cm³. The insulating film 116 is in contact withthe regions 108 n of the metal oxide 108. Thus, the concentration of animpurity (e.g., hydrogen) in the regions 108 n in contact with theinsulating film 116 is increased, leading to an increase in the carrierdensity of the regions 108 n.

[Fourth Insulating Film]

As the insulating film 118, an oxide insulating film can be used.Alternatively, a layered film of an oxide insulating film and a nitrideinsulating film can be used as the insulating film 118. The insulatingfilm 118 can be formed using, for example, silicon oxide, siliconoxynitride, silicon nitride oxide, aluminum oxide, hafnium oxide,gallium oxide, Ga—Zn oxide, or the like.

Furthermore, the insulating film 118 is preferably a film functioning asa barrier film against hydrogen, water, and the like from the outside.

The thickness of the insulating film 118 can be greater than or equal to30 nm and less than or equal to 500 nm, or greater than or equal to 100nm and less than or equal to 400 nm.

2-3. Structure Example 2 of Transistor

Next, a structure of a transistor different from that in FIGS. 6(A),6(B), and 6(C) will be described with reference to FIGS. 7(A), 7(B), and7(C)

FIG. 7(A) is a top view of the transistor 150; FIG. 7(B) is across-sectional view taken along dashed-dotted line X1-X2 in FIG. 7(A);and FIG. 7(C) is a cross-sectional view taken along dashed-dotted lineY1-Y2 in FIG. 7(A).

The transistor 150 illustrated in FIGS. 7(A), 7(B), and 7(C) includesthe conductive film 106 over the substrate 102; the insulating film 104over the conductive film 106; the metal oxide 108 over the insulatingfilm 104; the insulating film 110 over the metal oxide 108; theconductive film 112 over the insulating film 110; and the insulatingfilm 116 over the insulating film 104, the metal oxide 108, and theconductive film 112.

Note that the metal oxide 108 has a structure similar to that in thetransistor 100 shown in FIGS. 6(A), 6(B), and 6(C). The transistor 150shown in FIGS. 7(A), 7(B), and 7(C) includes the conductive film 106 andan opening 143 in addition to the components of the transistor 100described above.

The opening 143 is provided in the insulating films 104 and 110. Theconductive film 106 is electrically connected to the conductive film 112through the opening 143. Thus, the same potential is applied to theconductive film 106 and the conductive film 112. Note that differentpotentials may be applied to the conductive film 106 and the conductivefilm 112 without providing the opening 143. Alternatively, theconductive film 106 may be used as a light-blocking film withoutproviding the opening 143. When the conductive film 106 is formed usinga light-blocking material, for example, light from the bottom with whichthe metal oxide 108 is irradiated can be reduced.

In the case of the structure of the transistor 150, the conductive film106 functions as a first gate electrode (also referred to as abottom-gate electrode), and the conductive film 112 functions as asecond gate electrode (also referred to as a top-gate electrode). Theinsulating film 104 functions as a first gate insulating film, and theinsulating film 110 functions as a second gate insulating film.

The conductive film 106 can be formed using a material similar to theabove-described materials of the conductive films 112, 120 a, and 120 b.It is particularly suitable to use a material containing copper forformation of the conductive film 106 because the resistance can bereduced. It is favorable that, for example, the conductive film 106 havea stacked-layer structure in which a copper film is provided over atitanium nitride film, a tantalum nitride film, or a tungsten film, andthat the conductive films 120 a and 120 b have a stacked-layer structurein which a copper film is provided over a titanium nitride film, atantalum nitride film, or a tungsten film. In that case, by using thetransistor 150 as one or both of a pixel transistor and a drivingtransistor of a display device, parasitic capacitance generated betweenthe conductive film 106 and the conductive film 120 a and parasiticcapacitance generated between the conductive film 106 and the conductivefilm 120 b can be reduced. Thus, the conductive film 106, the conductivefilm 120 a, and the conductive film 120 b can be used not only as thefirst gate electrode, the source electrode, and the drain electrode ofthe transistor 150, but also as power supply wirings, signal supplywirings, connection wirings, or the like of the display device.

In this manner, unlike the transistor 100 described above, thetransistor 150 in FIGS. 7(A), 7(B), and 7(C) has a structure including aconductive film functioning as a gate electrode over and under the metaloxide 108. As in the transistor 150, a semiconductor device of oneembodiment of the present invention may be provided with a plurality ofgate electrodes.

As illustrated in FIGS. 7(B) and 7(C), the metal oxide 108 is positionedto face each of the conductive film 106 functioning as a first gateelectrode and the conductive film 112 functioning as a second gateelectrode and is sandwiched between the two conductive films functioningas the gate electrodes.

Furthermore, the length of the conductive film 112 in the channel widthdirection is larger than the length of the metal oxide 108 in thechannel width direction. In the channel width direction, the whole metaloxide 108 is covered with the conductive film 112 with the insulatingfilm 110 placed therebetween. Since the conductive film 112 is connectedto the conductive film 106 through the opening 143 provided in theinsulating film 104 and the insulating film 110, one of side surfaces ofthe metal oxide 108 in the channel width direction faces the conductivefilm 112 with the insulating film 110 placed therebetween.

In other words, the conductive film 106 and the conductive film 112 areconnected through the opening 143 provided in the insulating films 104and 110, and each include a region positioned outside a side edgeportion of the metal oxide 108.

Such a structure enables the metal oxide 108 included in the transistor150 to be electrically surrounded by electric fields of the conductivefilm 106 functioning as a first gate electrode and the conductive film112 functioning as a second gate electrode. A device structure of atransistor, like that of the transistor 150, in which electric fields ofthe first gate electrode and the second gate electrode electricallysurround the metal oxide 108 where a channel region is formed can bereferred to as a Surrounded channel (S-channel) structure.

Since the transistor 150 has the S-channel structure, an electric fieldfor inducing a channel can be effectively applied to the metal oxide 108by the conductive film 106 or the conductive film 112; thus, the currentdrive capability of the transistor 150 can be improved and high on-statecurrent characteristics can be obtained. Since the on-state current canbe increased, it is possible to reduce the size of the transistor 150.Furthermore, since the transistor 150 has a structure in which the metaloxide 108 is surrounded by the conductive film 106 and the conductivefilm 112, the mechanical strength of the transistor 150 can beincreased.

Note that in the channel width direction of the transistor 150, anopening different from the opening 143 may be formed on the side of themetal oxide 108 on which the opening 143 is not formed.

When a transistor has a pair of gate electrodes between which asemiconductor film is positioned as in the transistor 150, one of thegate electrodes may be supplied with a signal A, and the other gateelectrode may be supplied with a fixed potential V_(b). Alternatively,one of the gate electrodes may be supplied with the signal A, and theother gate electrode may be supplied with a signal B. Alternatively, oneof the gate electrodes may be supplied with a fixed potential V_(a), andthe other gate electrode may be supplied with the fixed potential V_(b).

The signal A is, for example, a signal for controlling the on state orthe off state. The signal A may be a digital signal with two kinds ofpotentials, a potential V1 and a potential V2 (V1>V2). For example, thepotential V1 can be a high power supply potential, and the potential V2can be a low power supply potential. The signal A may be an analogsignal.

The fixed potential V_(b) is, for example, a potential for controlling athreshold voltage V_(thA) of the transistor. The fixed potential V_(b)may be the potential V1 or the potential V2. In that case, a potentialgenerator circuit for generating the fixed potential V_(b) is notnecessarily provided separately, which is preferable. The fixedpotential V_(b) may be a potential different from the potential V1 orthe potential V2. When the fixed potential V_(b) is low, the thresholdvoltage V_(thA) can be high in some cases. As a result, the draincurrent when the gate-source voltage V_(g)s is 0 V can be reduced, andleakage current in a circuit including the transistor can be reduced insome cases. The fixed potential V_(b) may be, for example, lower thanthe low power supply potential. Meanwhile, a high fixed potential V_(b)can lower the threshold voltage V_(thA) in some cases. As a result, thedrain current when the gate-source voltage V_(g)s is a high power supplypotential can be increased and the operating speed of the circuitincluding the transistor can be increased in some cases. The fixedpotential V_(b) may be, for example, higher than the low power supplypotential.

The signal B is, for example, a signal for controlling the on state orthe off state. The signal B may be a digital signal with two kinds ofpotentials, a potential V3 and a potential V4 (V3>V4). For example, thepotential V3 can be a high power supply potential, and the potential V4can be a low power supply potential. The signal B may be an analogsignal.

When both the signal A and the signal B are digital signals, the signalB may be a signal having the same digital value as the signal A. In thiscase, it may be possible to increase the on-state current of thetransistor and increase the operating speed of the circuit including thetransistor. Here, the potential V1 and the potential V2 of the signal Amay be different from the potential V3 and the potential V4 of thesignal B. For example, if a gate insulating film for the gate to whichthe signal B is input is thicker than a gate insulating film for thegate to which the signal A is input, the potential amplitude of thesignal B (V3−V4) may be larger than the potential amplitude of thesignal A (V1−V2). In this manner, the influence of the signal A and theinfluence of the signal B on the on state or the off state of thetransistor can be substantially the same in some cases.

When both the signal A and the signal B are digital signals, the signalB may be a signal having a digital value different from that of thesignal A. In this case, the signal A and the signal B can separatelycontrol the transistor, and thus, higher performance can be achieved insome cases. The transistor which is, for example, an n-channeltransistor can function by itself as a NAND circuit, a NOR circuit, orthe like in the following case: the transistor is turned on only whenthe signal A has the potential V1 and the signal B has the potential V3,or the transistor is turned off only when the signal A has the potentialV2 and the signal B has the potential V4. The signal B may be a signalfor controlling the threshold voltage V_(thA). The signal B may be asignal whose potential is different between a period in which thecircuit including the transistor operates and a period in which thecircuit does not operate. The signal B may be a signal whose potentialvaries depending on the operation mode of the circuit. In this case, thepotential of the signal B is not changed as frequently as the potentialof the signal A in some cases.

When both the signal A and the signal B are analog signals, the signal Bmay be an analog signal having the same potential as the signal A, ananalog signal whose potential is a constant times the potential of thesignal A, an analog signal whose potential is higher or lower than thepotential of the signal A by a constant, or the like. In this case, itmay be possible to increase the on-state current of the transistor andincrease the operating speed of the circuit including the transistor.The signal B may be an analog signal different from the signal A. Inthis case, the signal A and the signal B can separately control thetransistor, and thus, higher performance can be achieved in some cases.

The signal A may be a digital signal, and the signal B may be an analogsignal. Alternatively, the signal A may be an analog signal, and thesignal B may be a digital signal.

When both of the gate electrodes of the transistor are supplied with thefixed potentials, the transistor can function as an element equivalentto a resistor in some cases. For example, in the case where thetransistor is of an n-channel type, the effective resistance of thetransistor can be sometimes low (high) when the fixed potential V_(a) orthe fixed potential V_(b) is high (low). When both the fixed potentialV_(a) and the fixed potential V_(b) are high (low), the effectiveresistance lower (higher) than the effective resistance of a transistorwith only one gate can be obtained in some cases.

Note that the other components of the transistor 150 are similar tothose of the transistor 100 described above and have similar effects.

An insulating film may further be formed over the transistor 150. Thetransistor 150 illustrated in FIGS. 7(A), 7(B), and 7(C) includes aninsulating film 122 over the conductive films 120 a and 120 b and theinsulating film 118.

The insulating film 122 has a function of covering unevenness and thelike caused by the transistor or the like. The insulating film 122 hasan insulating property and is formed using an inorganic material or anorganic material. Examples of the inorganic material include a siliconoxide film, a silicon oxynitride film, a silicon nitride oxide film, asilicon nitride film, an aluminum oxide film, and an aluminum nitridefilm. Examples of the organic material include photosensitive resinmaterials such as an acrylic resin and a polyimide resin.

2-4. Structure Example 3 of Transistor

Next, a structure different from that of the transistor 150 in FIGS.7(A), 7(B), and 7(C) will be described with reference to FIG. 8 .

FIGS. 8(A) and 8(B) are cross-sectional views of a transistor 160. Notethat the top view of the transistor 160 is similar to that of thetransistor 150 in FIG. 7(A), and therefore the description is omittedhere.

The transistor 160 illustrated in FIGS. 8(A) and 8(B) is different fromthe transistor 150 in the stacked-layer structure of the conductive film112, the shape of the conductive film 112, and the shape of theinsulating film 110.

The conductive film 112 in the transistor 160 includes a conductive film112_1 over the insulating film 110 and a conductive film 112_2 over theconductive film 112_1. For example, an oxide conductive film is used asthe conductive film 112_1, so that excess oxygen can be added to theinsulating film 110. The oxide conductive film is formed by a sputteringmethod in an atmosphere containing an oxygen gas. As the oxideconductive film, an oxide including indium and tin, an oxide includingtungsten and indium, an oxide including tungsten, indium, and zinc, anoxide including titanium and indium, an oxide including titanium,indium, and tin, an oxide including indium and zinc, an oxide includingsilicon, indium, and tin, an oxide including indium, gallium, and zinc,or the like can be used, for example.

As illustrated in FIG. 8(B), the conductive film 112_2 is connected tothe conductive film 106 through the opening 143. When the opening 143 isformed, the opening 143 is formed after a conductive film to be theconductive film 112_1 is formed, so that the shape illustrated in FIG.8(B) can be obtained. In the case where an oxide conductive film is usedas the conductive film 112_1, the structure in which the conductive film112_2 is connected to the conductive film 106 can reduces the contactresistance between the conductive film 112 and the conductive film 106.

The conductive film 112 and the insulating film 110 in the transistor160 have a tapered shape. More specifically, the lower edge portion ofthe conductive film 112 is formed outside the upper edge portion of theconductive film 112. The lower edge portion of the insulating film 110is formed outside the upper edge portion of the insulating film 110. Inaddition, the lower edge portion of the conductive film 112 is formed insubstantially the same position as that of the upper edge portion of theinsulating film 110.

The transistor 160 in which the conductive film 112 and the insulatingfilm 110 have a tapered shape is suitable because coverage with theinsulating film 116 can be increased as compared with the transistor 160in which the conductive film 112 and the insulating film 110 have arectangular shape.

Note that the other components of the transistor 160 are similar tothose of the transistor 150 described above and have similar effects.

2-5. Method for Manufacturing Semiconductor Device

Next, an example of a method for manufacturing the transistor 150illustrated in FIGS. 7(A), 7(B), and 7(C) will be described withreference to FIG. 9 to FIG. 11 . Note that FIG. 9 to FIG. 11 arecross-sectional views in the channel length direction and the channelwidth direction illustrating the method for manufacturing the transistor150.

First, the conductive film 106 is formed over the substrate 102. Next,the insulating film 104 is formed over the substrate 102 and theconductive film 106, and a metal oxide film is formed over theinsulating film 104. Then, the metal oxide film is processed into anisland shape, whereby a metal oxide 108 a is formed (see FIG. 9(A)).

The conductive film 106 can be formed by selecting the above-mentionedmaterials. In this embodiment, as the conductive film 106, a stackedfilm of a 50-nm-thick tungsten film and a 400-nm-thick copper film isformed with a sputtering apparatus.

Note that as a method for processing a conductive film to be theconductive film 106, one or both of a wet etching method and a dryetching method can be used. In this embodiment, the conductive film isprocessed by etching the copper film by a wet etching method and thenetching the tungsten film by a dry etching method to form the conductivefilm 106.

The insulating film 104 can be formed by a sputtering method, a CVDmethod, an evaporation method, a pulsed laser deposition (PLD) method, aprinting method, a coating method, or the like as appropriate. In thisembodiment, as the insulating film 104, a 400-nm-thick silicon nitridefilm and a 50-nm-thick silicon oxynitride film are formed with a PECVDapparatus.

After the insulating film 104 is formed, oxygen may be added to theinsulating film 104. As oxygen added to the insulating film 104, anoxygen radical, an oxygen atom, an oxygen atomic ion, an oxygenmolecular ion, or the like may be used. As an addition method, an iondoping method, an ion implantation method, a plasma treatment method, orthe like is given. Alternatively, a film that suppresses oxygen releasemay be formed over the insulating film 104, and then oxygen may be addedto the insulating film 104 through the film.

The film that suppresses oxygen release can be formed using a conductivefilm or a semiconductor film containing one or more of indium, zinc,gallium, tin, aluminum, chromium, tantalum, titanium, molybdenum,nickel, iron, cobalt, and tungsten.

In the case where oxygen is added by plasma treatment, oxygen is excitedby a microwave to generate high-density oxygen plasma, whereby theamount of oxygen added to the insulating film 104 can be increased.

In forming the metal oxide 108 a, an inert gas (e.g., a helium gas, anargon gas, or a xenon gas) may be mixed in addition to the oxygen gas.Note that the proportion of the oxygen gas in the whole deposition gas(hereinafter also referred to as an oxygen flow rate ratio) in formingthe metal oxide 108 a is higher than or equal to 0% and lower than orequal to 30%, preferably higher than or equal to 5% and lower than orequal to 20%.

Conditions for forming the metal oxide 108 a are as follows: thesubstrate temperature is higher than or equal to room temperature andlower than or equal to 180° C., and the substrate temperature ispreferably higher than or equal to room temperature and lower than orequal to 140° C. The substrate temperature at the time of forming themetal oxide 108 a is preferably, for example, higher than or equal toroom temperature and lower than 140° C. because the productivity isincreased.

The thickness of the metal oxide 108 a is greater than or equal to 3 nmand less than or equal to 200 nm, preferably greater than or equal to 3nm and less than or equal to 100 nm, further preferably greater than orequal to 3 nm and less than or equal to 60 nm.

Note that in the case where a large-sized glass substrate (e.g., the 6thgeneration to the 10th generation) is used as the substrate 102 and inthe case where the substrate temperature in forming the metal oxide 108a is higher than or equal to 200° C. and lower than or equal to 300° C.,the substrate 102 might be changed in shape (distorted or warped).Therefore, in the case where a large-sized glass substrate is used, thechange in the shape of the glass substrate can be suppressed by settingthe substrate temperature in forming the metal oxide 108 a to higherthan or equal to room temperature and lower than 200° C.

In addition, increasing the purity of the sputtering gas is necessary.For example, as an oxygen gas or an argon gas used for a sputtering gas,a gas highly purified to have a dew point of −40° C. or lower,preferably −80° C. or lower, further preferably −100° C. or lower, stillfurther preferably −120° C. or lower is used, whereby entry of moistureor the like into the metal oxide can be prevented as much as possible.

In the case where the metal oxide film is formed by a sputtering method,a chamber in a sputtering apparatus is preferably evacuated to be a highvacuum (to the degree of about 5×10⁻⁷ Pa to 1×10⁻⁴ Pa) with anadsorption vacuum evacuation pump such as a cryopump in order to removewater or the like, which serves as an impurity for the metal oxide, asmuch as possible. In particular, the partial pressure of gas moleculescorresponding to H₂O (gas molecules corresponding to m/z=18) in thechamber in the standby mode of the sputtering apparatus is preferablylower than or equal to 1×10⁻⁴ Pa, further preferably lower than or equalto 5×10⁻⁵ Pa.

In this embodiment, the formation conditions of the metal oxide 108 aare as follows.

The metal oxide 108 a is formed under the following formationconditions: an In—Ga—Zn metal oxide target is used and a sputteringmethod is used. The substrate temperature and the oxygen flow rate ratioat the time of film formation of the metal oxide 108 a can be set asappropriate. The pressure in a chamber is 0.6 Pa, and an AC power of2500 W is supplied to the metal oxide target provided in the sputteringapparatus, whereby the oxide is formed.

Note that to process the formed metal oxide film into the metal oxide108 a, one or both of a wet etching method and a dry etching method canbe used.

After the metal oxide 108 a is formed, heat treatment may be performedto dehydrate or dehydrogenate the metal oxide 108 a. The temperature ofthe heat treatment is typically higher than or equal to 150° C. andlower than the strain point of the substrate, higher than or equal to250° C. and lower than or equal to 450° C., or higher than or equal to300° C. and lower than or equal to 450° C.

The heat treatment can be performed in an inert atmosphere containingnitrogen or a rare gas such as helium, neon, argon, xenon, or krypton.Alternatively, heating may be performed in an inert atmosphere, and thenheating may be performed in an oxygen atmosphere. Note that it ispreferable that the above inert atmosphere and oxygen atmosphere notcontain hydrogen, water, or the like. The treatment time may be longerthan or equal to 3 minutes and shorter than or equal to 24 hours.

An electric furnace, an RTA apparatus, or the like can be used for theheat treatment. With the use of an RTA apparatus, the heat treatment canbe performed at a temperature higher than or equal to the strain pointof the substrate only for a short time. Therefore, the heat treatmenttime can be shortened.

When the metal oxide film is formed while being heated or heat treatmentis performed after the metal oxide is formed, the hydrogen concentrationin the metal oxide, which is measured by SIMS, can be 5×10¹⁹ atoms/cm³or lower, 1×10¹⁹ atoms/cm³ or lower, 5×10¹⁸ atoms/cm³ or lower, 1×10¹⁸atoms/cm³ or lower, 5×10¹⁷ atoms/cm³ or lower, or 1×10¹⁶ atoms/cm³ orlower.

Next, an insulating film 110_0 is formed over the insulating film 104and the metal oxide 108 a (see FIG. 9(B)).

As the insulating film 110_0, a silicon oxide film or a siliconoxynitride film can be formed with a plasma-enhanced chemical vapordeposition apparatus (also referred to as a PECVD apparatus or simply aplasma CVD apparatus). In this case, a deposition gas containing siliconand an oxidizing gas are preferably used as a source gas. Typicalexamples of the deposition gas containing silicon include silane,disilane, trisilane, and silane fluoride. Examples of the oxidizing gasinclude oxygen, ozone, dinitrogen monoxide, and nitrogen dioxide.

A silicon oxynitride film having a small amount of defects can be formedas the insulating film 110_0 with the PECVD apparatus in which the flowrate of the oxidizing gas is more than 20 times and less than 100 times,or more than or equal to 40 times and less than or equal to 80 times theflow rate of the deposition gas and the pressure in a treatment chamberis lower than 100 Pa or lower than or equal to 50 Pa.

As the insulating film 110_0, a dense silicon oxide film or a densesilicon oxynitride film can be formed under the following conditions:the substrate placed in a vacuum-evacuated treatment chamber of thePECVD apparatus is held at a temperature higher than or equal to 280° C.and lower than or equal to 400° C.; the pressure in the treatmentchamber into which a source gas is introduced is set to be higher thanor equal to 20 Pa and lower than or equal to 250 Pa, preferably higherthan or equal to 100 Pa and lower than or equal to 250 Pa; and ahigh-frequency power is supplied to an electrode provided in thetreatment chamber.

The insulating film 110_0 may be formed by a PECVD method using amicrowave. A microwave refers to a wave in the frequency range of 300MHz to 300 GHz. In the case of using a microwave, electron temperatureand electron energy are low. Furthermore, in supplied power, theproportion of power used for acceleration of electrons is low, and powercan be used for dissociation and ionization of more molecules; thus,plasma with a high density (high-density plasma) can be excited.Accordingly, with little plasma damage to the deposition surface or adeposit, the insulating film 110_0 having few defects can be formed.

Alternatively, the insulating film 110_0 can be formed by a CVD methodusing an organosilane gas. As the organosilane gas, any of the followingsilicon-containing compounds can be used: tetraethyl orthosilicate(TEOS: chemical formula Si(OC₂H₅)₄); tetramethylsilane (TMS: chemicalformula Si(CH₃)₄); tetramethylcyclotetrasiloxane (TMCTS);octamethylcyclotetrasiloxane (OMCTS); hexamethyldisilazane (HMDS);triethoxysilane (SiH(OC₂H₅)₃); trisdimethylaminosilane (SiH(N(CH₃)₂)₃);and the like. The insulating film 110_0 having high coverage can beformed by a CVD method using an organosilane gas.

In this embodiment, as the insulating film 110_0, a 100-nm-thick siliconoxynitride film is formed with the PECVD apparatus.

Subsequently, a mask is formed by lithography in a desired position overthe insulating film 110_0, and then the insulating film 110_0 and theinsulating film 104 are partly etched, so that the opening 143 reachingthe conductive film 106 is formed (see FIG. 9(C)).

To form the opening 143, one or both of a wet etching method and a dryetching method can be used. In this embodiment, the opening 143 isformed by a dry etching method.

Next, a conductive film 112_0 is formed over the conductive film 106 andthe insulating film 110_0 so as to cover the opening 143. In the casewhere a metal oxide film is used as the conductive film 112_0, forexample, oxygen might be added to the insulating film 110_0 during theformation of the conductive film 112_0 (see FIG. 9(D)).

Note that in FIG. 9(D), oxygen added to the insulating film 110_0 isschematically shown by arrows. Furthermore, the conductive film 112_0formed to cover the opening 143 is electrically connected to theconductive film 106.

In the case where a metal oxide film is used as the conductive film112_0, the conductive film 112_0 is preferably formed by a sputteringmethod in an atmosphere containing an oxygen gas. Formation of theconductive film 112_0 in an atmosphere containing an oxygen gas allowssuitable addition of oxygen to the insulating film 110_0. Note that amethod for forming the conductive film 112_0 is not limited to asputtering method, and another method such as an ALD method may be used.

In this embodiment, a 100-nm-thick IGZO film containing an In—Ga—Znoxide (In:Ga:Zn=4:2:4.1 (atomic ratio)) is formed as the conductive film112_0 by a sputtering method. Oxygen addition treatment may be performedon the insulating film 110_0 before or after the formation of theconductive film 112_0. The oxygen addition treatment can be performed ina manner similar to that of the oxygen addition treatment that can beperformed after the formation of the insulating film 104.

Subsequently, a mask 140 is formed by a lithography process in a desiredposition over the conductive film 112_0 (see FIG. 10(A)).

Next, etching is performed from above the mask 140 to process theconductive film 112_0 and the insulating film 110_0. After theprocessing of the conductive film 112_0 and the insulating film 110_0,the mask 140 is removed. As a result of the processing of the conductivefilm 112_0 and the insulating film 110_0, the island-shaped conductivefilm 112 and the island-shaped insulating film 110 are formed (see FIG.10(B)).

In this embodiment, the conductive film 112_0 and the insulating film110_0 are processed by a dry etching method.

In the processing of the conductive film 112_0 and the insulating film110_0, the thickness of the metal oxide 108 a in a region notoverlapping with the conductive film 112 is reduced in some cases. Inother cases, in the processing of the conductive film 112_0 and theinsulating film 110_0, the thickness of the insulating film 104 in aregion not overlapping with the metal oxide 108 a is reduced. In theprocessing of the conductive film 112_0 and the insulating film 110_0,an etchant or an etching gas (e.g., chlorine) might be added to themetal oxide 108 a or the constituent element of the conductive film112_0 or the insulating film 110_0 might be added to the metal oxide108.

Next, the insulating film 116 is formed over the insulating film 104,the metal oxide 108, and the conductive film 112. By the formation ofthe insulating film 116, part of the metal oxide 108 a that is incontact with the insulating film 116 becomes the regions 108 n. Here,the metal oxide 108 a overlapping with the conductive film 112 is themetal oxide 108 (see FIG. 10(C)).

The insulating film 116 can be formed using a material selected from theabove-mentioned materials. In this embodiment, as the insulating film116, a 100-nm-thick silicon nitride oxide film is formed with a PECVDapparatus. In the formation of the silicon nitride oxide film, twosteps, i.e., plasma treatment and deposition treatment, are performed ata temperature of 220° C. The plasma treatment is performed under thefollowing conditions: an argon gas at a flow rate of 100 sccm and anitrogen gas at a flow rate of 1000 sccm are introduced into a chamberbefore deposition; the pressure in the chamber is set to 40 Pa; and apower of 1000 W is supplied to an RF power source (27.12 MHz). Thedeposition treatment is performed under the following conditions: asilane gas at a flow rate of 50 sccm, a nitrogen gas at a flow rate of5000 sccm, and an ammonia gas at a flow rate of 100 sccm are introducedinto the chamber; the pressure in the chamber is set to 100 Pa; and apower of 1000 W is supplied to the RF power source (27.12 MHz).

When a silicon nitride oxide film is used as the insulating film 116,nitrogen or hydrogen in the silicon nitride oxide film can be suppliedto the regions 108 n in contact with the insulating film 116. Inaddition, when the formation temperature of the insulating film 116 isthe above temperature, release of excess oxygen contained in theinsulating film 110 to the outside can be suppressed.

Next, the insulating film 118 is formed over the insulating film 116(see FIG. 11(A)).

The insulating film 118 can be formed using a material selected from theabove-mentioned materials. In this embodiment, as the insulating film118, a 300-nm-thick silicon oxynitride film is formed with a PECVDapparatus.

Subsequently, a mask is formed by lithography in a desired position overthe insulating film 118, and then the insulating film 118 and theinsulating film 116 are partly etched, so that the opening 141 a and theopening 141 b reaching the regions 108 n are formed (see FIG. 11(B)).

To etch the insulating film 118 and the insulating film 116, one or bothof a wet etching method and a dry etching method can be used. In thisembodiment, the insulating film 118 and the insulating film 116 areprocessed by a dry etching method.

Next, a conductive film is formed over the regions 108 n and theinsulating film 118 so as to cover the openings 141 a and 141 b, and theconductive film is processed into a desired shape, whereby theconductive films 120 a and 120 b are formed (see FIG. 11(C)).

The conductive films 120 a and 120 b can be formed by selecting theabove-mentioned materials. In this embodiment, as the conductive films120 a and 120 b, a stacked film of a 50-nm-thick tungsten film and a400-nm-thick copper film is formed with a sputtering apparatus.

Note that as a method for processing a conductive film to be theconductive films 120 a and 120 b, one or both of a wet etching methodand a dry etching method can be used. In this embodiment, the conductivefilm is processed by etching the copper film by a wet etching method andthen etching the tungsten film by a dry etching method to form theconductive films 120 a and 120 b.

Then, the insulating film 122 is formed to cover the conductive films120 a and 120 b and the insulating film 118.

Through the above steps, the transistor 150 shown in FIGS. 7(A), 7(B),and 7(C) can be manufactured.

Note that the films included in the transistor 150 (the insulating film,the metal oxide film, the conductive film, and the like) can be formedby, other than the above methods, a sputtering method, a chemical vapordeposition (CVD) method, a vacuum evaporation method, a pulsed laserdeposition (PLD) method, or an ALD method. Alternatively, a coatingmethod or a printing method can be used. Although a sputtering methodand a plasma-enhanced chemical vapor deposition (PECVD) method aretypical examples of the deposition method, a thermal CVD method may beused. As an example of a thermal CVD method, a metal organic chemicalvapor deposition (MOCVD) method can be given.

Deposition by the thermal CVD method may be performed in such a mannerthat the pressure in a chamber is set to an atmospheric pressure or areduced pressure, and a source gas and an oxidizer are supplied to thechamber at a time and react with each other in the vicinity of thesubstrate or over the substrate. Thus, no plasma is generated in thedeposition; therefore, the thermal CVD method has an advantage that nodefect due to plasma damage is caused.

The films such as the conductive films, the insulating films, and themetal oxide films that are described above can be formed by a thermalCVD method such as an MOCVD method.

For example, in the case where a hafnium oxide film is formed with adeposition apparatus employing an ALD method, two kinds of gases areused, namely, ozone (O₃) as an oxidizer and a source gas that isobtained by vaporizing liquid containing a solvent and a hafniumprecursor (hafnium alkoxide or hafnium amide such astetrakis(dimethylamide)hafnium (TDMAH, Hf[N(CH₃)₂]₄) ortetrakis(ethylmethylamide)hafnium).

In the case where an aluminum oxide film is formed with a depositionapparatus employing an ALD method, two kinds of gases are used, namely,H₂O as an oxidizer and a source gas that is obtained by vaporizingliquid containing a solvent and an aluminum precursor (e.g.,trimethylaluminum (TMA, Al(CH₃)₃)). Examples of another material includetris(dimethylamide)aluminum, triisobutylaluminum, and aluminumtris(2,2,6,6-tetramethyl-3,5-heptanedionate).

In the case where a silicon oxide film is formed with a depositionapparatus employing an ALD method, hexachlorodisilane is adsorbed on asurface on which a film is to be formed, and radicals of an oxidizinggas (O₂ or dinitrogen monoxide) are supplied to react with theadsorbate.

In the case where a tungsten film is formed with a deposition apparatusemploying an ALD method, a WF₆ gas and a B₂H₆ gas are sequentiallyintroduced to form an initial tungsten film, and then, a WF₆ gas and anH₂ gas are used to form a tungsten film. Note that an SiH₄ gas may beused instead of a B₂H₆ gas.

In the case where a metal oxide such as an In—Ga—Zn—O film is formedwith a deposition apparatus employing an ALD method, an In(CH₃)₃ gas andan O₃ gas) are used to form an In—O layer, a Ga(CH₃)₃ gas and an O₃ gas)are used to form a GaO layer, and then, a Zn(CH₃)₂ gas and an O₃ gas)are used to form a ZnO layer. Note that the order of these layers is notlimited to this example. A mixed compound layer such as an In—Ga—Olayer, an In—Zn—O layer, or a Ga—Zn—O layer may be formed by using thesegases. Note that although an H₂O gas that is obtained by bubbling waterwith an inert gas such as Ar may be used instead of an O₃ gas), it ispreferable to use an O₃ gas), which does not contain H.

2-6. Structure Example 4 of Transistor

FIG. 12(A) is a top view of a transistor 300A; FIG. 12(B) is across-sectional view taken along dashed-dotted line X1-X2 in FIG. 12(A);and FIG. 12(C) is a cross-sectional view taken along dashed-dotted lineY1-Y2 in FIG. 12(A). Note that in FIG. 12(A), some components of thetransistor 300A (e.g., an insulating film functioning as a gateinsulating film) are not illustrated to avoid complexity. The directionof the dashed-dotted line X1-X2 may be referred to as a channel lengthdirection, and the direction of the dashed-dotted line Y1-Y2 may bereferred to as a channel width direction. As in FIG. 12(A), somecomponents are not illustrated in some cases in top views of transistorsdescribed below.

The transistor 300A illustrated in FIG. 12 includes a conductive film304 over a substrate 302, an insulating film 306 over the substrate 302and the conductive film 304, an insulating film 307 over the insulatingfilm 306, a metal oxide 308 over the insulating film 307, a conductivefilm 312 a over the metal oxide 308, and a conductive film 312 b overthe metal oxide 308. Over the transistor 300A, specifically, over theconductive films 312 a and 312 b and the metal oxide 308, insulatingfilms 314 and 316, and an insulating film 318 are provided.

In the transistor 300A, the insulating films 306 and 307 function as thegate insulating films of the transistor 300A, and the insulating films314, 316, and 318 function as protective insulating films of thetransistor 300A. Furthermore, in the transistor 300A, the conductivefilm 304 functions as a gate electrode, the conductive film 312 afunctions as a source electrode, and the conductive film 312 b functionsas a drain electrode.

In this specification and the like, the insulating films 306 and 307 maybe referred to as a first insulating film, the insulating films 314 and316 may be referred to as a second insulating film, and the insulatingfilm 318 may be referred to as a third insulating film.

The transistor 300A illustrated in FIG. 12 is a channel-etchedtransistor. The metal oxide of one embodiment of the present inventionis suitable for a channel-etched transistor.

2-7. Structure Example 5 of Transistor

FIG. 13(A) is a top view of a transistor 300B; FIG. 13(B) is across-sectional view taken along dashed-dotted line X1-X2 in FIG. 13(A);and FIG. 13(C) is a cross-sectional view taken along dashed-dotted lineY1-Y2 in FIG. 13(A).

The transistor 300B illustrated in FIG. 13 includes the conductive film304 over the substrate 302, the insulating film 306 over the substrate302 and the conductive film 304, the insulating film 307 over theinsulating film 306, the metal oxide 308 over the insulating film 307,the insulating film 314 over the metal oxide 308, the insulating film316 over the insulating film 314, the conductive film 312 a electricallyconnected to the metal oxide 308 through an opening 341 a provided inthe insulating film 314 and the insulating film 316, and the conductivefilm 312 b electrically connected to the metal oxide 308 through anopening 341 b provided in the insulating film 314 and the insulatingfilm 316. Over the transistor 300B, specifically, over the conductivefilms 312 a and 312 b and the insulating film 316, the insulating film318 is provided.

In the transistor 300B, the insulating films 306 and 307 each functionas a gate insulating film of the transistor 300B, the insulating films314 and 316 each function as a protective insulating film of the metaloxide 308, and the insulating film 318 functions as a protectiveinsulating film of the transistor 300B. Moreover, in the transistor300B, the conductive film 304 functions as a gate electrode, theconductive film 312 a functions as a source electrode, and theconductive film 312 b functions as a drain electrode.

The transistor 300A illustrated in FIG. 12 has a channel-etchedstructure, whereas the transistor 300B in FIGS. 13(A), 13(B), and 13(C)has a channel-protective structure. The metal oxide of one embodiment ofthe present invention is suitable for a channel-protective transistor aswell.

2-8. Structure Example 6 of Transistor

FIG. 14(A) is a top view of a transistor 300C; FIG. 14(B) is across-sectional view taken along dashed-dotted line X1-X2 in FIG. 14(A);and FIG. 14(C) is a cross-sectional view taken along dashed-dotted lineY1-Y2 in FIG. 14(A).

The transistor 300C illustrated in FIG. 14 is different from thetransistor 300B in FIGS. 13(A), 13(B), and 13(C) in the shapes of theinsulating films 314 and 316. Specifically, the insulating films 314 and316 of the transistor 300C have island shapes and are provided over achannel region of the metal oxide 308. Other components are similar tothose of the transistor 300B.

2-9. Structure Example 7 of Transistor

FIG. 15(A) is a top view of a transistor 300D; FIG. 15(B) is across-sectional view taken along dashed-dotted line X1-X2 in FIG. 15(A);and FIG. 15(C) is a cross-sectional view taken along dashed-dotted lineY1-Y2 in FIG. 15(A).

The transistor 300D illustrated in FIG. 15 includes the conductive film304 over the substrate 302, the insulating film 306 over the substrate302 and the conductive film 304, the insulating film 307 over theinsulating film 306, the metal oxide 308 over the insulating film 307,the conductive film 312 a over the metal oxide 308, the conductive film312 b over the metal oxide 308, the insulating film 314 over the metaloxide 308 and the conductive films 312 a and 312 b, the insulating film316 over the insulating film 314, the insulating film 318 over theinsulating film 316, and conductive films 320 a and 320 b over theinsulating film 318.

In the transistor 300D, the insulating films 306 and 307 function asfirst gate insulating films of the transistor 300D, and the insulatingfilms 314, 316, and 318 function as second gate insulating films of thetransistor 300D. Furthermore, in the transistor 300D, the conductivefilm 304 functions as a first gate electrode, the conductive film 320 afunctions as a second gate electrode, and the conductive film 320 bfunctions as a pixel electrode used for a display device. The conductivefilm 312 a functions as a source electrode, and the conductive film 312b functions as a drain electrode.

As illustrated in FIG. 15(C), the conductive film 320 b is connected tothe conductive film 304 in openings 342 b and 342 c provided in theinsulating films 306, 307, 314, 316, and 318. Thus, the same potentialis applied to the conductive film 320 b and the conductive film 304.

The structure of the transistor 300D is not limited to that describedabove, in which the openings 342 b and 342 c are provided so that theconductive film 320 b is connected to the conductive film 304. Forexample, a structure in which only one of the opening 342 b or theopening 342 c is provided so that the conductive film 320 b is connectedto the conductive film 304, or a structure in which the conductive film320 b is not connected to the conductive film 304 without providing theopening 342 b and the opening 342 c may be employed. Note that in thecase where the conductive film 320 b is not connected to the conductivefilm 304, it is possible to apply different potentials to the conductivefilm 320 b and the conductive film 304.

The conductive film 320 b is connected to the conductive film 312 bthrough an opening 342 a provided in the insulating films 314, 316, and318.

Note that the transistor 300D has the S-channel structure describedabove.

At least part of this embodiment can be implemented in combination withany of the other embodiments described in this specification asappropriate.

Embodiment 3

In this embodiment, an example of a display panel which can be used fora display portion or the like in a display device including thesemiconductor device of one embodiment of the present invention isdescribed with reference to FIG. 17 and FIG. 18 . The display paneldescribed below as an example includes both a reflective liquid crystalelement and a light-emitting element and can display an image in boththe transmissive mode and the reflective mode. Note that the metal oxideof one embodiment of the present invention and a transistor includingthe metal oxide can be preferably used in a transistor in a pixel of adisplay device, a driver for driving the display device, an LSIsupplying data to the display device, or the like.

Structure Example of Display Panel

FIG. 17 is a schematic perspective view of a display panel 600 of oneembodiment of the present invention. In the display panel 600, asubstrate 651 and a substrate 661 are attached to each other. In FIG. 17, the substrate 661 is denoted by a dashed line.

The display panel 600 includes a display portion 662, a circuit 659, awiring 666, and the like. The substrate 651 is provided with the circuit659, the wiring 666, a conductive film 663 that serves as a pixelelectrode, and the like. FIG. 17 shows an example in which an IC 673 andan FPC 672 are mounted on the substrate 651. Thus, the structure shownin FIG. 17 can be referred to as a display module including the displaypanel 600, the FPC 672, and the IC 673.

As the circuit 659, for example, a circuit functioning as a scan linedriver circuit can be used.

The wiring 666 has a function of supplying a signal or electric power tothe display portion 662 or the circuit 659. The signal or electric poweris input to the wiring 666 from the outside through the FPC 672 or fromthe IC 673.

FIG. 17 shows an example in which the IC 673 is provided on thesubstrate 651 by a chip on glass (COG) method or the like. As the IC673, an IC functioning as a scan line driver circuit, a signal linedriver circuit, or the like can be used. Note that it is possible thatthe IC 673 is not provided when, for example, the display panel 600includes circuits serving as a scan line driver circuit and a signalline driver circuit and when the circuits serving as a scan line drivercircuit and a signal line driver circuit are provided outside and asignal for driving the display panel 600 is input through the FPC 672.Alternatively, the IC 673 may be mounted on the FPC 672 by a chip onfilm (COF) method or the like.

FIG. 17 also shows an enlarged view of part of the display portion 662.The conductive films 663 included in a plurality of display elements arearranged in a matrix in the display portion 662. The conductive film 663has a function of reflecting visible light and serves as a reflectiveelectrode of a liquid crystal element 640 described later.

As shown in FIG. 17 , the conductive film 663 has an opening. Alight-emitting element 660 is positioned closer to the substrate 651than the conductive film 663 is. Light is emitted from thelight-emitting element 660 to the substrate 661 side through the openingin the conductive film 663.

Cross-Sectional Structure Example

FIG. 18 shows an example of cross sections of part of a region includingthe FPC 672, part of a region including the circuit 659, and part of aregion including the display portion 662 of the display panel 600illustrated in FIG. 17 .

The display panel 600 includes an insulating film 620 between thesubstrate 651 and the substrate 661. The display panel 600 also includesthe light-emitting element 660, a transistor 601, a transistor 605, atransistor 606, a coloring layer 634, and the like between the substrate651 and the insulating film 620. Furthermore, the display panel 600includes the liquid crystal element 640, a coloring layer 631, and thelike between the insulating film 620 and the substrate 661. Thesubstrate 661 and the insulating film 620 are bonded with an adhesivelayer 641. The substrate 651 and the insulating film 620 are bonded withan adhesive layer 642.

The transistor 606 is electrically connected to the liquid crystalelement 640 and the transistor 605 is electrically connected to thelight-emitting element 660. Since the transistor 605 and the transistor606 are formed on a surface of the insulating film 620 which is on thesubstrate 651 side, the transistors 605 and 606 can be formed throughthe same process.

The substrate 661 is provided with the coloring layer 631, alight-blocking film 632, an insulating film 621, a conductive film 613serving as a common electrode of the liquid crystal element 640, analignment film 633 b, an insulating film 617, and the like. Theinsulating film 617 serves as a spacer for holding a cell gap of theliquid crystal element 640.

Insulating layers such as an insulating film 681, an insulating film682, an insulating film 683, an insulating film 684, and an insulatingfilm 685 are provided on the substrate 651 side of the insulating film620. Part of the insulating film 681 functions as a gate insulatinglayer of each transistor. The insulating film 682, the insulating film683, and the insulating film 684 are provided to cover each transistor.The insulating film 685 is provided to cover the insulating film 684.The insulating film 684 and the insulating film 685 each function as aplanarization layer. Note that an example where the three insulatinglayers, the insulating film 682, the insulating film 683, and theinsulating film 684, are provided to cover the transistors and the likeis described here; however, one embodiment of the present invention isnot limited to this, and four or more insulating layers, a singleinsulating layer, or two insulating layers may be provided. Theinsulating film 684 functioning as a planarization layer is notnecessarily provided when not needed.

The transistor 601, the transistor 605, and the transistor 606 eachinclude a conductive film 654 part of which functions as a gate, aconductive film 652 part of which functions as a source or a drain, anda semiconductor film 653. Here, a plurality of layers obtained byprocessing the same conductive film are shown with the same hatchingpattern.

The liquid crystal element 640 is a reflective liquid crystal element.The liquid crystal element 640 has a stacked structure of a conductivefilm 635, a liquid crystal layer 612, and the conductive film 613. Inaddition, the conductive film 663 which reflects visible light isprovided in contact with the surface of the conductive film 635 thatfaces the substrate 651. The conductive film 663 includes an opening655. The conductive film 635 and the conductive film 613 contain amaterial transmitting visible light. In addition, an alignment film 633a is provided between the liquid crystal layer 612 and the conductivefilm 635 and the alignment film 633 b is provided between the liquidcrystal layer 612 and the conductive film 613. A polarizing plate 656 isprovided on an outer surface of the substrate 661.

In the liquid crystal element 640, the conductive film 663 has afunction of reflecting visible light and the conductive film 613 has afunction of transmitting visible light. Light entering from thesubstrate 661 side is polarized by the polarizing plate 656, passesthrough the conductive film 613 and the liquid crystal layer 612, and isreflected by the conductive film 663. Then, the light passes through theliquid crystal layer 612 and the conductive film 613 again and reachesthe polarizing plate 656. In this case, alignment of the liquid crystalis controlled with a voltage that is applied between the conductive film613 and each of the conductive film 663 and the conductive film 635, andthus optical modulation of light can be controlled. That is, theintensity of light emitted through the polarizing plate 656 can becontrolled. Light excluding light in a particular wavelength region isabsorbed by the coloring layer 631, and thus, emitted light is redlight, for example.

The light-emitting element 660 is a bottom-emission light-emittingelement. The light-emitting element 660 has a structure in which aconductive film 643, an EL layer 644, and a conductive film 645 b arestacked in this order from the insulating film 620 side. In addition, aconductive film 645 a is provided to cover the conductive film 645 b.The conductive film 645 b contains a material reflecting visible light,and the conductive film 643 and the conductive film 645 a contain amaterial transmitting visible light. Light is emitted from thelight-emitting element 660 to the substrate 661 side through thecoloring layer 634, the insulating film 620, the opening 655, theconductive film 613, and the like.

Here, as illustrated in FIG. 18 , the conductive film 635 transmittingvisible light is preferably provided for the opening 655. Accordingly,the liquid crystal is aligned in a region overlapping with the opening655 as well as in the other regions, in which case an alignment defectof the liquid crystal is prevented from being generated in the boundaryportion of these regions and undesired light leakage can be suppressed.

As the polarizing plate 656 provided on an outer surface of thesubstrate 661, a linear polarizing plate or a circularly polarizingplate can be used. An example of a circularly polarizing plate is astack including a linear polarizing plate and a quarter-wave retardationplate. Such a structure can reduce reflection of external light. Thecell gap, alignment, drive voltage, and the like of the liquid crystalelement used as the liquid crystal element 640 are controlled dependingon the kind of the polarizing plate so that desirable contrast isobtained.

In addition, an insulating film 647 is provided on the insulating film646 covering an end portion of the conductive film 643. The insulatingfilm 647 has a function as a spacer for preventing the insulating film620 and the substrate 651 from getting closer than necessary. In thecase where the EL layer 644 or the conductive film 645 a is formed usinga blocking mask (metal mask), the insulating film 647 may have afunction as a spacer for preventing the blocking mask from being incontact with a surface on which the EL layer 644 or the conductive film645 a is formed. Note that the insulating film 647 is not necessarilyprovided when not needed.

One of a source and a drain of the transistor 605 is electricallyconnected to the conductive film 643 of the light-emitting element 660through a conductive film 648.

One of a source and a drain of the transistor 606 is electricallyconnected to the conductive film 663 through a connection portion 607.The conductive film 663 and the conductive film 635 are provided incontact with each other and electrically connected to each other. Here,in the connection portion 607, the conductive layers provided on bothsurfaces of the insulating film 620 are connected to each other throughan opening in the insulating film 620.

A connection portion 604 is provided in a region where the substrate 651and the substrate 661 do not overlap with each other. The connectionportion 604 is electrically connected to the FPC 672 through aconnection layer 649. The connection portion 604 has a structure similarto that of the connection portion 607. On the top surface of theconnection portion 604, a conductive layer obtained by processing thesame conductive film as the conductive film 635 is exposed. Thus, theconnection portion 604 and the FPC 672 can be electrically connected toeach other through the connection layer 649.

A connection portion 687 is provided in part of a region where theadhesive layer 641 is provided. In the connection portion 687, theconductive layer obtained by processing the same conductive film as theconductive film 635 is electrically connected to part of the conductivefilm 613 with a connector 686. Accordingly, a signal or a potentialinput from the FPC 672 connected to the substrate 651 side can besupplied to the conductive film 613 formed on the substrate 661 sidethrough the connection portion 687.

As the connector 686, a conductive particle can be used, for example. Asthe conductive particle, a particle of an organic resin, silica, or thelike coated with a metal material can be used. It is preferable to usenickel or gold as the metal material because contact resistance can bereduced. It is also preferable to use a particle coated with layers oftwo or more kinds of metal materials, such as a particle coated withnickel and further with gold. As the connector 686, a material capableof elastic deformation or plastic deformation is preferably used. Asshown in FIG. 18 , the connector 686 which is the conductive particlehas a shape that is vertically crushed in some cases. With the crushedshape, the contact area between the connector 686 and a conductive layerelectrically connected to the connector 686 can be increased, therebyreducing contact resistance and suppressing the generation of problemssuch as disconnection.

The connector 686 is preferably provided so as to be covered with theadhesive layer 641. For example, the connectors 686 are dispersed in theadhesive layer 641 before curing of the adhesive layer 641.

FIG. 18 shows an example of the circuit 659 in which the transistor 601is provided.

The structure in which the semiconductor film 653 where a channel isformed is provided between two gates is used as an example of thetransistor 601 and the transistor 605 in FIG. 18 . One gate is formedusing the conductive film 654 and the other gate is formed using aconductive film 623 overlapping with the semiconductor film 653 with theinsulating film 682 provided therebetween. Such a structure enablescontrol of threshold voltages of a transistor. In that case, the twogates may be connected to each other and supplied with the same signalto operate the transistor. Such a transistor can have higherfield-effect mobility and thus have higher on-state current than othertransistors. Consequently, a circuit capable of high-speed operation canbe obtained. Furthermore, the area occupied by a circuit portion can bereduced. The use of the transistor having a high on-state current canreduce signal delay in wirings and can reduce display unevenness even ina display panel in which the number of wirings is increased because ofincrease in size or resolution.

Note that the transistor included in the circuit 659 and the transistorincluded in the display portion 662 may have the same structure. Aplurality of transistors included in the circuit 659 may have the samestructure or different structures. A plurality of transistors includedin the display portion 662 may have the same structure or differentstructures.

A material through which impurities such as water and hydrogen do noteasily diffuse is preferably used for at least one of the insulatingfilm 682 and the insulating film 683 which cover the transistors. Thatis, the insulating film 682 or the insulating film 683 can function as abarrier film. Such a structure can effectively suppress diffusion of theimpurities into the transistors from the outside, and a highly reliabledisplay panel can be provided.

The insulating film 621 is provided on the substrate 661 side to coverthe coloring layer 631 and the light-blocking film 632. The insulatingfilm 621 may have a function as a planarization layer. The insulatingfilm 621 enables the conductive film 613 to have an almost flat surface,resulting in a uniform alignment state of the liquid crystal layer 612.

An example of the method for manufacturing the display panel 600 isdescribed. For example, the conductive film 635, the conductive film663, and the insulating film 620 are formed in this order over a supportsubstrate provided with a separation layer, and the transistor 605, thetransistor 606, the light-emitting element 660, and the like are formed.Then, the substrate 651 and the support substrate are bonded with theadhesive layer 642. After that, separation is performed at the interfacebetween the separation layer and each of the insulating film 620 and theconductive film 635, whereby the support substrate and the separationlayer are removed. Separately, the coloring layer 631, thelight-blocking film 632, the conductive film 613, and the like areformed over the substrate 661 in advance. Then, the liquid crystal isdropped onto the substrate 651 or the substrate 661 and the substrate651 and the substrate 661 are bonded with the adhesive layer 641,whereby the display panel 600 can be manufactured.

A material for the separation layer can be selected such that separationat the interface with the insulating film 620 and the conductive film635 occurs. In particular, it is preferable that a stacked layer of alayer including a high-melting-point metal material, such as tungsten,and a layer including an oxide of the metal material be used as theseparation layer, and a stacked layer of a plurality of layers, such asa silicon nitride layer, a silicon oxynitride layer, and a siliconnitride oxide layer, be used as the insulating film 620 over theseparation layer. The use of the high-melting-point metal material forthe separation layer can increase the formation temperature of a layerformed in a later step, which reduces impurity concentration andachieves a highly reliable display panel.

As the conductive film 635, an oxide or a nitride such as a metal oxideor a metal nitride is preferably used. In the case of using a metaloxide, a material in which at least one of the concentrations ofhydrogen, boron, phosphorus, nitrogen, and other impurities and thenumber of oxygen vacancies is made to be higher than those in asemiconductor layer of a transistor is used for the conductive film 635.

<Components>

The above components will be described below. Note that descriptions ofstructures having functions similar to those in the above embodimentsare omitted.

[Adhesive Layer]

As the adhesive layer, a variety of curable adhesives such as a reactivecurable adhesive, a thermosetting adhesive, an anaerobic adhesive, and aphotocurable adhesive such as an ultraviolet curable adhesive can beused. Examples of these adhesives include an epoxy resin, an acrylicresin, a silicone resin, a phenol resin, a polyimide resin, an imideresin, a polyvinyl chloride (PVC) resin, a polyvinyl butyral (PVB)resin, and an ethylene vinyl acetate (EVA) resin. In particular, amaterial with low moisture permeability, such as an epoxy resin, ispreferred. Alternatively, a two-component-mixture-type resin may beused. Further alternatively, an adhesive sheet or the like may be used.

Furthermore, the resin may include a drying agent. For example, asubstance that adsorbs moisture by chemical adsorption, such as an oxideof an alkaline earth metal (e.g., calcium oxide or barium oxide), can beused. Alternatively, a substance that adsorbs moisture by physicaladsorption, such as zeolite or silica gel, may be used. The drying agentis preferably included because it can prevent impurities such asmoisture from entering the element, thereby improving the reliability ofthe display panel.

In addition, it is preferable to mix a filler with a high refractiveindex or a light-scattering member into the resin, in which case lightextraction efficiency can be enhanced. For example, titanium oxide,barium oxide, zeolite, zirconium, or the like can be used.

[Connection Layer]

As the connection layer, an anisotropic conductive film (ACF), ananisotropic conductive paste (ACP), or the like can be used.

[Coloring Layer]

Examples of a material that can be used for the coloring layers includea metal material, a resin material, and a resin material containing apigment or dye.

[Light-Blocking Layer]

Examples of a material that can be used for the light-blocking layerinclude carbon black, titanium black, a metal, a metal oxide, and acomposite oxide containing a solid solution of a plurality of metaloxides. The light-blocking layer may be a film containing a resinmaterial or a thin film of an inorganic material such as a metal.Stacked films containing the material of the coloring layer can also beused for the light-blocking layer. For example, a stacked-layerstructure of a film containing a material of a coloring layer whichtransmits light of a certain color and a film containing a material of acoloring layer which transmits light of another color can be employed.It is preferable that the coloring layer and the light-blocking layer beformed using the same material because the same manufacturing apparatuscan be used and the process can be simplified.

The above is the description of the components.

Manufacturing Method Example

A manufacturing method example of a display panel using a flexiblesubstrate is described.

Here, layers including a display element, a circuit, a wiring, anelectrode, optical members such as a coloring layer and a light-blockinglayer, an insulating layer, and the like, are collectively referred toas an element layer. The element layer includes, for example, a displayelement, and may additionally include a wiring electrically connected tothe display element or an element such as a transistor used in a pixelor a circuit.

In addition, here, a flexible member which supports the element layer ata stage at which the display element is completed (the manufacturingprocess is finished) is referred to as a substrate. For example, asubstrate includes an extremely thin film with a thickness greater thanor equal to 10 nm and less than or equal to 300 μm.

As a method for forming an element layer over a flexible substrateprovided with an insulating surface, typically, there are two methodsshown below. One of them is to directly form an element layer over thesubstrate. The other method is to form an element layer over a supportsubstrate that is different from the substrate and then to separate theelement layer from the support substrate to be transferred to thesubstrate. Although not described in detail here, in addition to theabove two methods, there is a method in which an element layer is formedover a substrate which does not have flexibility and the substrate isthinned by polishing or the like to have flexibility.

In the case where a material of the substrate can withstand heatingtemperature in a process for forming the element layer, it is preferablethat the element layer be formed directly over the substrate, in whichcase a manufacturing process can be simplified. At this time, theelement layer is preferably formed in a state where the substrate isfixed to the support substrate, in which case transfer thereof in anapparatus and between apparatuses can be easy.

In the case of employing the method in which the element layer is formedover the support substrate and then transferred to the substrate, first,a separation layer and an insulating layer are stacked over the supportsubstrate, and then the element layer is formed over the insulatinglayer. Next, the element layer is separated from the support substrateand then transferred to the substrate. At this time, selected is amaterial with which separation at an interface between the supportsubstrate and the separation layer, at an interface between theseparation layer and the insulating layer, or in the separation layeroccurs. With the method, it is preferable that a material having highheat resistance be used for the support substrate or the separationlayer, in which case the upper limit of the temperature applied when theelement layer is formed can be increased, and an element layer includinga more highly reliable element can be formed.

For example, it is preferable that a stack of a layer containing ahigh-melting-point metal material, such as tungsten, and a layercontaining an oxide of the metal material be used as the separationlayer, and a stack of a plurality of layers, such as silicon oxide,silicon nitride, silicon oxynitride, and silicon nitride oxide, be usedas the insulating layer over the separation layer.

As the method for separating the support substrate from the elementlayer, applying mechanical force, etching the separation layer, andmaking a liquid permeate the separation interface are given as examples.Alternatively, separation may be performed by heating or cooling twolayers of the separation interface by utilizing a difference in thermalexpansion coefficient.

The separation layer is not necessarily provided in the case where theseparation can be performed at an interface between the supportsubstrate and the insulating layer.

For example, glass and an organic resin such as polyimide can be used asthe support substrate and the insulating layer, respectively. In thatcase, a separation trigger may be formed by, for example, locallyheating part of the organic resin with laser light or the like, or byphysically cutting part of or making a hole through the organic resinwith a sharp tool, and separation may be performed at an interfacebetween the glass and the organic resin. As the above-described organicresin, a photosensitive material is preferably used because an openingor the like can be easily formed. The above-described laser lightpreferably has a wavelength region, for example, from visible light toultraviolet light. For example, light having a wavelength of greaterthan or equal to 200 nm and less than or equal to 400 nm, preferablygreater than or equal to 250 nm and less than or equal to 350 nm can beused. In particular, an excimer laser having a wavelength of 308 nm ispreferably used because the productivity is increased. Alternatively, asolid-state UV laser (also referred to as a semiconductor UV laser),such as a UV laser having a wavelength of 355 nm which is the thirdharmonic of an Nd:YAG laser, may be used.

Alternatively, a heat-generation layer may be provided between thesupport substrate and the insulating layer formed of an organic resin,and separation may be performed at an interface between theheat-generation layer and the insulating layer by heating theheat-generation layer. For the heat-generation layer, any of a varietyof materials such as a material which generates heat by feeding current,a material which generates heat by absorbing light, and a material whichgenerates heat by applying a magnetic field can be used. For example,for the heat-generation layer, a material selected from a semiconductor,a metal, and an insulator can be used.

In the above-described methods, the insulating layer formed of anorganic resin can be used as a substrate after the separation.

The above is the description of a manufacturing method of a flexibledisplay panel.

At least part of this embodiment can be implemented in combination withany of the other embodiments described in this specification asappropriate.

Embodiment 4

In this embodiment, a metal oxide of one embodiment of the presentinvention is described.

The metal oxide of one embodiment of the present invention includes In(indium), M (M is Al, Ga, Y, or Sn), and Zn (zinc). Specifically, M ispreferably Ga (gallium). In the following description, Ga is used as M.

Here, the case where silicon (Si), boron (B), or carbon (C) exists as animpurity in an In—Ga—Zn oxide is described.

<Calculation Model and Calculation Method>

First, calculations were performed using a reference model of anIn—Ga—Zn oxide in an amorphous state which has no impurities, a model inwhich one Si atom is added to the reference model, a model in which oneB atom is added to the reference model, and a model in which one C atomis added to the reference model.

Specifically, a model 700 with [In]:[Ga]:[Zn]:[O]=1:1:1:4 shown in FIG.19(A) was used as the reference crystal model. Note that the model 700includes 112 atoms.

Strictly, an In-M-Zn oxide having a CAC composition is not in anamorphous state. On the other hand, the In-M-Zn oxide having the CACcomposition has lower crystallinity than an In-M-Zn oxide having a CAACstructure. Accordingly, a model in an amorphous state was used forconvenience to reduce influence of the crystal structure and observe thebonding state.

In the model 700, a Si atom, a B atom, or a C atom was assumed to existas an impurity, and one Si atom, one B atom, or one C atom was locatedin an interstitial site of the model 700. Note that one impurity wasadded to the model 700 including the 112 atoms. Accordingly, theimpurity concentration of the model is approximately 7×10²⁰ [atoms/cm³].

FIG. 20(A) shows a local structure 702 of the vicinity of Si, which isextracted from a model in which the Si atom is bonded to four O atoms inthe case where Si exists as an impurity, and FIG. 20(C) shows a localstructure 704 of the vicinity of Si, which is extracted from a model inwhich the Si atom is bonded to three O atoms and one Ga atom.

FIG. 21(A) shows a local structure 706 of the vicinity of a B atom,which is extracted from a model in which the B atom is bonded to three Oatoms in the case where B exists as an impurity, and FIG. 21(C) shows alocal structure 708 of the vicinity of B, which is extracted from themodel.

FIG. 22(A) shows a local structure 710 of the vicinity of a C atom,which is extracted from a model in which the C atom is bonded to two Oatoms and one Ga atom in the case where C exists as an impurity, andFIG. 22(C) shows a local structure 712 of the vicinity of a C atom,which is extracted from a model in which the C atom is bonded to one Oatom and one Ga atom.

The specific calculation is as follows. A first principle electronicstate calculation package, VASP (Vienna Ab initio Simulation Package),was used for the atomic relaxation calculation. The calculationconditions are listed in the following table.

TABLE 1 Software VASP Exchange-correlation functional GGA-PBEPseudopotential PAW method Cut-off energy of plane wave 800 ev SamplingStructure optimization 1 × 1 × 1 point k Density of states 2 × 2 × 2<Density of States>

FIG. 19(B) shows the density of states in FIG. 19(A). In FIG. 19(B), theFermi level (the energy of the highest occupied level of electrons) isadjusted to be 0 eV in the horizontal axis. It was found from FIG. 19(B)that the electrons reach the valence band maximum and the level in thegap does not exist.

FIG. 20(B) and FIG. 20(D) show the density of states in the case whereone Si atom is added as an impurity. Note that FIG. 20(B) shows thedensity of states in the case where the local structure 702 shown inFIG. 20(A) is included. FIG. 20(D) shows the density of states in thecase where the local structure 704 shown in FIG. 20(C) is included.

It was found from FIG. 20(B) and FIG. 20(D) that when a Si atom exists,the Fermi level is located in the conduction band. This indicates thatcarriers are generated in an In—Ga—Zn oxide (the In—Ga—Zn oxide is madeto be an n-type) owing to Si atoms.

FIG. 21(B) and FIG. 21(D) show the density of states in the case whereone B atom is added as an impurity. Note that FIG. 21(B) shows thedensity of states in the case where the local structure 706 shown inFIG. 21(A) is included. FIG. 21(D) shows the density of states in thecase where the local structure 708 shown in FIG. 21(C) is included.

It was found from FIG. 21(B) and FIG. 21(D) that when a B atom exists,the Fermi level is located in the conduction band. This indicates thatcarriers are generated in an In—Ga—Zn oxide (the In—Ga—Zn oxide is madeto be an n-type) owing to B atoms.

FIG. 22(B) and FIG. 22(D) show the density of states in the case whereone C atom is added as an impurity. Note that FIG. 22(B) shows thedensity of states in the case where the local structure 710 shown inFIG. 22(A) is included. FIG. 22(D) shows the density of states in thecase where the local structure 712 shown in FIG. 22(C) is included.

It was found from FIG. 22(B) and FIG. 22(D) that when a C atom exists,the Fermi level is located in the conduction band. This indicates thatcarriers are generated in an In—Ga—Zn oxide (the In—Ga—Zn oxide is madeto be an n-type) owing to C atoms.

It is highly probable that Si atoms and B atoms exist as cations in anIn—Ga—Zn oxide because the electronegativities of Si and B are closer tothe electronegativities of In, Ga, and Zn than the electronegativity ofO. Thus, it is supposed that carriers are generated.

Although C is bonded to a metal and O because the electronegativity of Cis between the electronegativity of O and the electronegativities of In,Ga, and Zn, it is assumed that C is likely to exist as cationsbasically.

Furthermore, a Si atom, a B atom, and a C atom are more strongly bondedto an O atom than an In atom, a Ga atom, and a Zn atom are. For thatreason, by the entry of a Si atom, a B atom, and a C atom, O atomsbonded to an In atom, a Ga atom, and a Zn atom are trapped by the Siatom, the B atom, and the C atom. It is thus presumed that deep levelscorresponding to oxygen vacancies are formed.

The structure and method described in this embodiment can be implementedby being combined as appropriate with any of the other structures andmethods described in the other embodiments.

Example 1

In this example, a metal oxide of one embodiment of the presentinvention, which was formed over a substrate, was measured with avariety of methods, and the measurement results are described. Note thatin this example, Sample 1A, Sample 1B, Sample 1C, Sample 1D, Sample 1E,Sample 1F, Sample 1G, Sample 1H, and Sample 1J, and Sample 1X, Sample1Y, and Sample 1Z were fabricated.

<Structure of Samples and Fabrication Method Thereof>

Sample 1A, Sample 1B, Sample 1C, Sample 1D, Sample 1E, Sample 1F, Sample1G, Sample 1H, and Sample 1J, and Sample 1X, Sample 1Y, and Sample 1Zrelating to one embodiment of the present invention will be describedbelow. Sample 1A to Sample 1J and Sample 1X to Sample 1Z each include asubstrate and a metal oxide over the substrate. Note that Sample 1A toSample 1J are different from Sample 1X to Sample 1Z in the thickness ofthe metal oxide.

A 100-nm-thick metal oxide film was formed for Sample 1A to Sample 1J.Sample 1A to Sample 1J were fabricated at different temperatures anddifferent oxygen flow rate ratios in formation of the metal oxide film.

Meanwhile, a 500-nm-thick metal oxide film was formed for Sample 1X toSample 1Z. Sample 1X to Sample 1Z were fabricated at differenttemperatures and different oxygen flow rate ratios in formation of themetal oxide film.

The temperatures and the oxygen flow rate ratios in formation of themetal oxide films of Sample 1A to Sample 1J and Sample 1X to Sample 1Zare shown in the following table.

TABLE 2 O₂ Formation Film Flow rate [sccm] ratio temperature thicknessO₂ Ar [%] [° C.] [nm] Sample 1A 30 270 10 R.T. 100 Sample 1B 90 210 30R.T. 100 Sample 1C 300 0 100 R.T. 100 Sample 1D 30 270 10 130 100 Sample1E 90 210 30 130 100 Sample 1F 300 0 100 130 100 Sample 1G 30 270 10 170100 Sample 1H 90 210 30 170 100 Sample 1J 300 0 100 170 100 Sample 1X 30270 10 R.T. 500 Sample 1Y 30 270 10 130 500 Sample 1Z 300 0 100 170 500

Next, methods for fabricating the samples will be described.

A glass substrate was used as the substrate. Over the substrate, anIn—Ga—Zn oxide was formed as a metal oxide with a sputtering apparatus.The formation conditions were as follows: the pressure in a chamber was0.6 Pa; and a metal oxide target (an atomic ratio of In:Ga:Zn=4:2:4.1)was used as a target. The metal oxide target provided in the sputteringapparatus was supplied with an AC power of 2500 W, so that the metaloxide film was formed.

The formation temperatures and oxygen flow rate ratios shown in theabove table were used as the conditions for forming metal oxide films tofabricate Sample 1A to Sample 1J and Sample 1X to Sample 1Z.

Through the above steps, Sample 1A to Sample 1J and Sample 1X to Sample1Z were fabricated.

<Analysis by X-Ray Photoelectron Spectroscopy Measurement>

In this section, the results of X-ray photoelectron spectroscopy (XPS)measurement performed on Sample 1A, Sample 1D, and Sample 1J aredescribed. Note that the measurement was performed using Quantera SXMmanufactured by PHI, Inc. The conditions were as follows: an X-raysource was monochromatic Al (1486.6 eV), a detected region was a circlewith a diameter of 100 μm, and the detection depth was greater than orequal to 4 nm and less than or equal to 5 nm at an extraction angle of45°. In the measurement spectrum, an In3d5/2 peak, a Ga3d peak, a Zn3ppeak, and an O1s peak were detected as correction references. Theproportion of each kind of atoms [atomic %] was calculated on the basisof the detected peaks.

FIG. 23 shows XPS analysis results. Note that pie charts shown in FIG.23 were normalized on the assumption that the atomic ratio of In was 4.

As shown in FIG. 23 , neither the atomic ratio of Ga nor that of Zn wasan integer in the case where the charts were normalized on theassumption that the atomic ratio of In was an integer. Thus, it wasfound that the atomic ratios of Ga and Zn were non-integers in the casewhere the charts were normalized on the assumption that the atomic ratioof In was an integer.

It was also found that, in Sample 1A, Sample 1D, and Sample 1J, theatomic ratio of Ga in the formed metal oxide film was less than that ofGa in the metal oxide used as the target. In Sample 1J, the atomic ratioof Zn in the formed metal oxide film was [Zn]=3.21, which was less thanthe atomic ratio of Zn, [Zn]=4.1 in the metal oxide used as the target.Furthermore, in Sample 1J, which was formed at the highest temperature,the ratio of Zn in the formed metal oxide film tended to be smaller thanthat in Sample 1A and Sample 1D, which were formed at lower temperaturesthan Sample 1J. This is probably because Zn was volatilized when thefilm was formed while being heated.

<Analysis by X-Ray Diffraction>

In this section, results of X-ray diffraction (XRD) measurementperformed on the metal oxides over the glass substrates will bedescribed.

First, XRD analysis was performed on Sample 1A to Sample 1J by a powdermethod. As an XRD apparatus, D8 ADVANCE manufactured by Bruker AXS GmbHwas used. The conditions were as follows: scanning was performed by anout-of-plane method at θ/2θ; the scanning range was 15 deg. to 50 deg.;the step width was 0.01 deg.; and the accumulation time per point was0.1 sec.

FIG. 24 shows XRD spectra measured by an out-of-plane method. Note thatthe vertical axis represents intensity [a. u], and the horizontal axisrepresents an angle 2θ [deg.].

In the XRD spectra shown in FIG. 24 , the higher the substratetemperature at the time of film formation is or the higher the oxygengas flow rate ratio at the time of film formation is, the higher theintensity of the peak at around 2θ=31° is (in this example, greater thanor equal to 30° and less than or equal to 32°). Note that the peak ataround 2θ=31° is known to be derived from a crystalline IGZO compoundwhose c-axes are aligned in a direction substantially perpendicular to aformation surface or a top surface of the crystalline IGZO compound(such a compound is also referred to as CAAC-IGZO).

Also in the XRD spectra in FIG. 24 , as the substrate temperature at thetime of film formation is lower or the oxygen gas flow rate ratio at thetime of film formation is lower, a peak at around 2θ=31° becomes lessclear. Accordingly, it was found that there were no alignment in the a-bplane direction and c-axis alignment in the measured areas of thesamples that were formed at a lower substrate temperature or with alower oxygen gas flow rate ratio.

Here, in order to further analyze the metal oxide film formed under theconditions of Sample 1A, Sample 1D, and Sample 1J, XRD analysis wasperformed on Sample 1X, Sample 1Y, and Sample 1Z by a grazing incidenceXRD method (thin film method).

Note that SmartLab manufactured by Rigaku Corporation was used as theXRD apparatus. FIG. 25 shows a schematic view and setting of theapparatus. The output was set to 45 kV and 200 mA (a rotatinganticathode), and monochromatic X-ray was obtained with a Ge (220)monochrometer. The incident slit, the longitudinal slit, and theincident angle were set to 0.1 mm, 10 mm, and 0.5 deg., respectively.Alight-receiving slit 1 and a light-receiving slit 2 were opened, and alight-receiving solar slit was set to 0.5 deg.

As the measurement conditions, scanning was performed by an out-of-planemethod at 2θ/ω with an accumulation time per point of 100 sec. Here, thestep width was set to 0.1 deg. in the scanning range of 5 deg. to 45deg. The step width was set to 0.2 deg. in the scanning range of 45 deg.to 110 deg.

FIG. 26 shows the measurement results of XRD spectra. Note that thevertical axis represents intensity [a. u], and the horizontal axisrepresents an angle 2θ [deg.]. Note that in this specification, themaximum peak intensity is referred to as a peak intensity in some cases.

As shown in FIG. 26 , the peak intensity was detected between 2θ=31° and2θ=34° in Sample 1Z, Sample 1Y, and Sample 1X. Also in the XRD spectrain FIG. 26 , the highest peak intensity at around 2θ=31° was detected inSample 1Z, followed by Sample 1Y and Sample 1X. Note that the peak ataround 2θ=34° (in this example, greater than or equal to 33° and lessthan or equal to 35°) is known to be derived from a metal oxideincluding a nanocrystal (in particular, in the case where such a metaloxide has a function similar to that of a semiconductor, it is referredto as a nanocrystalline oxide semiconductor, hereinafter referred to asan nc-OS).

FIG. 26 shows the peak intensity detected between 2θ=31° and 2θ=34° inSample 1Z, Sample 1Y, and Sample 1X and asymmetric diffraction with theangle at which the peak intensity was detected as the symmetry axis.

FIG. 27 and FIG. 28 show the measurement results of XRD spectrum of eachof Sample 1Z, Sample 1Y, Sample 1X, and quartz glass as a comparativeexample. FIG. 27(A) and FIG. 27(B) show the measurement results ofSample 1Y, FIG. 27(C) and FIG. 27(D) show the measurement results ofSample 1Z, FIG. 28(A) and FIG. 28(B) show the measurement results ofquartz glass, and FIG. 28(C) and FIG. 28(D) show the measurement resultsof Sample 1X. Note that FIG. 27(B), FIG. 27(D), FIG. 28(B), and FIG.28(D) are enlarged views of regions denoted by dotted lines in FIG.27(A), FIG. 27(C), FIG. 28(A), and FIG. 28(C), respectively.

Here, the peak intensity between 2θ=31° and 2θ=34° was detected probablybecause of the synthesis of a peak of a crystalline IGZO compound whosepeak intensity is detected at 2θ=31° and a peak of a metal oxide (nc-OS)including a nanocrystal, whose peak intensity is detected at 2θ=34°.Thus, Sample 1Z and Sample 1Y are presumed to include the crystallineIGZO compound whose peak intensity is detected at 2θ=31° and the metaloxide (nc-OS) including a nanocrystal, whose peak intensity is detectedat 2θ=34°.

In Sample 1Z and Sample 1Y, the proportion of the metal oxide (nc-OS)including a nanocrystal is lower than that of the crystalline IGZOcompound, which probably results in the peak whose intensity is close to2θ=31° and which has a broader width toward 2θ=34°. Furthermore, Sample1Z has a higher proportion of the crystalline IGZO compound than Sample1Y, and thus, the peak intensity of Sample 1Z was probably detected atcloser to 2θ=31° than the peak intensity of Sample 1Y.

Meanwhile, in the measurement results of Sample 1X shown in FIG. 28(C)and FIG. 28(D), the peak intensity was detected at around 2θ=34° andasymmetric diffraction with the angle at which the peak intensity wasdetected as the symmetry axis was obtained. Sample 1A, which was formedunder the same formation condition of the metal oxide film as Sample 1X,did not have a clear peak in the XRD spectrum shown in FIG. 24 . Thatis, Sample 1X as well as Sample 1A is not presumed to have a clear peakderived from orientation in the a-b plane direction and the c-axisdirection in the measured area. In other words, Sample 1X is probably ametal oxide with low crystallinity.

As a comparative sample, the measurement results of quartz glass havingno crystallinity are shown in FIG. 28(A) and FIG. 28(B). The measurementresults of quartz glass show the peak intensity detected at around2θ=21° and symmetric diffraction with the angle at which the peakintensity was detected as the axis.

Meanwhile, unlike quartz glass, Sample 1X, which was considered to havelow crystallinity, showed asymmetric diffraction with the angle at whichthe peak intensity of the XRD spectrum was detected as the symmetryaxis. Thus, Sample 1X probably has a structure different from that ofquartz glass.

It was thus found that the peak intensity was detected between 2θ=31°and 2θ=34° in the XRD spectra of the metal oxide including thecrystalline IGZO compound and the metal oxide including a nanocrystal(nc-OS), and asymmetric diffraction with the angle at which the peakintensity was detected as the symmetry axis was obtained. It was alsofound that the metal oxide formed at a low substrate temperature or witha low oxygen gas flow rate ratio had asymmetric diffraction with theangle at which the peak intensity of the XRD spectrum was detected asthe symmetry axis, and had a structure different from that of quartzglass.

<TEM Images and Electron Diffraction>

This section describes the observation and analysis results of Sample1A, Sample 1D, and Sample 1J with a high-angle annular dark fieldscanning transmission electron microscope (HAADF-STEM) (hereinafter, animage obtained with a HAADF-STEM is also referred to as a TEM image).

This section also describes electron diffraction patterns obtained byirradiation of Sample 1A, Sample 1D, and Sample 1J with an electron beamwith a probe diameter of 1 nm (also referred to as a nanobeam electronbeam).

The plan-view TEM images were observed with a spherical aberrationcorrector function. The HAADF-STEM images were obtained using an atomicresolution analytical electron microscope JEM-ARM200F manufactured byJEOL Ltd. under the following conditions: the acceleration voltage was200 kV; and irradiation with an electron beam with a diameter ofapproximately 0.1 nmφ was performed.

Note that the electron diffraction patterns were observed while anelectron beam irradiation was performed at a constant rate from 0 secondto 35 seconds.

FIG. 29(A) shows a cross-sectional TEM image of Sample 1A, and FIG.29(B) shows an electron diffraction pattern of Sample 1A. FIG. 29(C)shows a cross-sectional TEM image of Sample 1D, and FIG. 29(D) shows anelectron diffraction pattern of Sample 1D. FIG. 29(E) shows across-sectional TEM image of Sample 1J, and FIG. 29(F) shows an electrondiffraction pattern of Sample 1J.

It is known that, for example, when an electron beam with a probediameter of 300 nm is incident on a CAAC-OS including an InGaZnO₄crystal in a direction parallel to the sample surface, a diffractionpattern including a spot derived from the (009) plane of the InGaZnO₄crystal is obtained. That is, the CAAC-OS has c-axis alignment and thec-axes are aligned in the direction substantially perpendicular to theformation surface or the top surface of the CAAC-OS. Meanwhile, aring-like diffraction pattern is shown when an electron beam with aprobe diameter of 300 nm is incident on the same sample in a directionperpendicular to the sample surface. That is, it is found that theCAAC-OS has neither a-axis alignment nor b-axis alignment.

Furthermore, a diffraction pattern like a halo pattern is observed whena metal oxide including a nanocrystal (in particular, in the case wheresuch a metal oxide has a function similar to that of a semiconductor, itis referred to as a nanocrystalline oxide semiconductor (nc-OS)) issubjected to electron diffraction using an electron beam with a largeprobe diameter (e.g., 50 nm or larger). Meanwhile, bright spots areobserved in a nanobeam electron diffraction pattern of the metal oxideincluding a nanocrystal found using an electron beam with a small probediameter (e.g., smaller than 50 nm). Furthermore, in a nanobeam electrondiffraction pattern of the metal oxide including a nanocrystal, a regionwith high luminance in a circular (ring) pattern is shown in some cases.In addition, a plurality of bright spots are shown in a ring-like shapein some cases.

A nanocrystal (hereinafter, also referred to as nc) was found in Sample1A from the result of the cross-sectional TEM observation as shown inFIG. 29(A). As shown in FIG. 29(B), the observed electron diffractionpattern of Sample 1A has a region with high luminance in a circular(ring) pattern. Furthermore, a plurality of spots were observed in thering-shaped region.

Sample 1D was found to have a CAAC structure and a nanocrystal from theresult of the cross-sectional TEM observation shown in FIG. 29(C). Asshown in FIG. 29(D), the observed electron diffraction pattern of Sample1D has a region with high luminance in a circular (ring) pattern.Furthermore, a plurality of spots were observed in the ring-shapedregion. In the diffraction pattern, spots derived from the (009) planewere slightly observed.

Meanwhile, Sample 1J was clearly found to have layered arrangement of aCAAC structure from the result of the cross-sectional TEM observation inFIG. 29(E). Furthermore, spots derived from the (009) plane were clearlyobserved from the result of the electron diffraction pattern of Sample1J shown in FIG. 29(F).

The features observed in the cross-sectional TEM images and theplan-view TEM images are one aspect of a structure of a metal oxide.

Next, electron diffraction patterns obtained by irradiation of Sample 1Awith an electron beam with a probe diameter of 1 nm (also referred to asa nanobeam electron beam) are shown in FIG. 30 .

Electron diffraction patterns of a black dot a1, a black dot a2, a blackdot a3, a black dot a4, and a black dot a5 in the plan-view TEM image ofSample 1A in FIG. 30(A) were observed. Note that the electrondiffraction patterns were observed while electron beam irradiation wasperformed at a constant rate from 0 second to 35 seconds. FIG. 30(C),FIG. 30(D), FIG. 30(E), FIG. 30(F), and FIG. 30(G) show the results ofthe black dot a1, the black dot a2, the black dot a3, the black dot a4,and the black dot a5, respectively.

In FIG. 30(C), FIG. 30(D), FIG. 30(E), FIG. 30(F), and FIG. 30(G),regions with high luminance in a ring pattern were observed.Furthermore, a plurality of spots were observed in the ring-shapedregions.

Electron diffraction patterns of a black dot b1, a black dot b2, a blackdot b3, a black dot b4, and a black dot b5 in the cross-sectional TEMimage of Sample 1A in FIG. 30(B) are observed. FIG. 30(H), FIG. 30(I),FIG. 30(J), FIG. 30(K), and FIG. 30(L) show the results of the black dotb1, the black dot b2, the black dot b3, the black dot b4, and the blackdot b5, respectively.

In FIG. 30(H), FIG. 30(I), FIG. 30(J), FIG. 30(K), and FIG. 30(L),regions with high luminance in a ring pattern were observed.Furthermore, a plurality of spots were observed in the ring-shapedregions.

That is, it was found that Sample 1A had an nc structure and hadcharacteristics distinctly different from those of a metal oxide havingan amorphous structure and those of a metal oxide having a singlecrystal structure.

As described above, the electron diffraction patterns of Sample 1A andSample 1D each have a region with high luminance in a ring pattern and aplurality of bright spots appeared in the ring-shaped region. It wasthus found that Sample 1A exhibits an electron diffraction pattern ofthe metal oxide including nanocrystals and does not show alignment inthe plane direction and the cross-sectional direction. Sample 1D wasfound to be a mixed material of the nc structure and the CAAC structure.

Meanwhile, the electron diffraction pattern of Sample 1J includes spotsderived from the (009) plane of an InGaZnO₄ crystal. It was thus foundthat Sample 1J had c-axis alignment and the c-axes were aligned in thedirection substantially perpendicular to the formation surface or thetop surface of Sample 1J.

<Analysis of TEM Image>

This section describes the observation and analysis results of Sample1A, Sample 1C, Sample 1D, Sample 1F, and Sample 1G with an HAADF-STEM.

The results of image analysis of plan-view TEM images are described. Theplan-view TEM images were obtained with a spherical aberration correctorfunction. The plan-view TEM images were obtained using an atomicresolution analytical electron microscope JEM-ARM200F manufactured byJEOL Ltd. under the following conditions: the acceleration voltage was200 kV; and irradiation with an electron beam with a diameter ofapproximately 0.1 nmφ was performed.

FIG. 31 shows the plan-view TEM images of Sample 1A, Sample 1C, Sample1D, Sample 1F, Sample 1G, and Sample 1J and images obtained throughimage processing of the plan-view TEM images. Note that in a table inFIG. 31 , left views are the plan-view TEM images and right views arethe images obtained through image processing of the plan-view TEM imageson the left side.

Image processing and image analyzing methods are described. First, asimage processing, the plan-view TEM image in FIG. 31 was subjected tofast Fourier transform (FFT), so that an FFT image was obtained. Then,the obtained FFT image was subjected to mask processing except for arange from 2.8 nm⁻¹ to 5.0 nm⁻¹. After that, the FFT image subjected tomask processing was subjected to inverse fast Fourier transform (IFFT)to obtain an FFT filtering image.

To conduct the image analysis, first, lattice points were extracted fromthe FFT filtering image. The extraction of lattice points was performedin the following manner. First, noise in the FFT filtering image wasremoved. To remove the noise, the luminance of a region within a 0.05-nmradius was smoothed using the following formula.

$\begin{matrix}\left\lbrack {{Formula}1} \right\rbrack &  \\{{{S\_{Int}}\left( {x,y} \right)} = {\sum\limits_{r \leq 0.05}\frac{{Int}\left( {x^{\prime},y^{\prime}} \right)}{r}}} & (1)\end{matrix}$

Here, S_Int(x,y) represents the smoothed luminance at the coordinates(x,y), r represents the distance between the coordinates (x,y) and thecoordinates (x′,y′), and Int(x′,y′) represents the luminance at thecoordinates (x′,y′). In the calculation, r is regarded as 1 when it is0.

Then, a search for lattice points was conducted. The coordinates withthe highest luminance among candidate lattice points within a 0.22-nmradius were regarded as the lattice point. At this point, a candidatelattice point was extracted. Within a 0.22-nm radius, detection errorsof lattice points due to noise can be less frequent. Note that adjacentlattice points are a certain distance away from each other in the TEMimage; thus, two or more lattice points are unlikely to be observedwithin a 0.22-nm radius.

Subsequently, coordinates with the highest luminance within a 0.22-nmradius from the extracted candidate lattice point were extracted toredetermine a candidate lattice point. The extraction of a candidatelattice point was repeated in this manner until no new candidate latticepoint appeared; the coordinates at that point were determined as latticepoints. Similarly, determination of another lattice point was performedat a position 0.22 nm or more away from the determined lattice point;thus, lattice points were determined in the entire region. Thedetermined lattice points are collectively called a lattice point group.

Next, a method for deriving an orientation of a hexagonal lattice fromthe extracted lattice point group is described with reference toschematic diagrams in FIG. 32(A), FIGS. 32(B), and 32(C) and a flowchart in FIG. 32(D). First, a reference lattice point was determined andthe six closest lattice points to the reference lattice point wereconnected to form a hexagonal lattice (see FIG. 32(A) and Step S101 inFIG. 32(D)). After that, an average distance R between the referencelattice point, which was the center point of the hexagonal lattice, andeach of the lattice points, which is a vertex, was calculated. Then, aregular hexagon was formed with the use of the reference lattice pointas the center point and the calculated distance R as the distance fromthe center point to each vertex (see FIG. 32(B) and Step S102 in FIG.32(D)). The distances from the vertices of the regular hexagon to theirrespective closest lattice points were regarded as a distance d1, adistance d2, a distance d3, a distance d4, a distance d5, and a distanced6 (see Step S103 in FIG. 32(D)). Next, the regular hexagon was rotatedaround the center point through 60° by 0.1°, and the average deviationbetween the hexagonal lattice and the rotated regular hexagon[D=(d1+d2+d3+d4+d5+d6)/6] was calculated (see Step S104 in FIG. 32(D)).Then, a rotation angle θ of the regular hexagon when the averagedeviation D becomes minimum was calculated as the orientation of thehexagonal lattice (see FIG. 32(C) and Step S105 in FIG. 32(D)).

Next, an observation area of the plan-view TEM image was adjusted sothat hexagonal lattices whose orientations were 30° account for thehighest percentage. Here, the average orientation of hexagonal latticewithin a 1-nm radius was calculated. The plan-view TEM image obtainedthrough image processing was then shown in such a manner that color orgradation changes in accordance with the angle of the hexagonal latticein the region. The image obtained through image processing of theplan-view TEM image in FIG. 31 is an image obtained by performing imageanalysis on the plan-view TEM image in FIG. 31 by the above method andapplying gradation in accordance with the angle of the hexagonallattice. In other words, the image obtained through the image processingof the plan-view TEM image is an image in which the orientations oflattice points in certain wavenumber ranges are extracted bycolor-coding the certain wavenumber ranges in an FFT filtering image ofthe plan-view TEM image.

As shown in FIG. 31 , in Sample 1A and Sample 1D in which nc wasobserved, the hexagons were oriented randomly and distributed in amosaic pattern. In Sample 1J in which a layered structure was observedin the cross-sectional TEM image, regions with uniformly orientedhexagons exist in a large area of several tens of nanometers. It wasfound that Sample 1D included an nc region in a random mosaic patternand a large-area region with uniform orientation as in Sample 1J.

It was found from FIG. 31 that as the substrate temperature at the timeof film formation is lower or the oxygen gas flow rate ratio at the timeof film formation is lower, regions in which the hexagons are orientedrandomly and distributed in a mosaic pattern are likely to exist.

Through the analysis of a plan-view TEM image of a CAAC-OS, a boundaryportion where angles of hexagonal lattices change can be examined.

Next, Voronoi diagrams were formed using lattice point groups in Sample1A. A Voronoi diagram is an image partitioned by regions including alattice point group. Each lattice point is closer to regions surroundingthe lattice point than to any other lattice point. A method for forminga Voronoi diagram is described below in detail using schematic diagramsin FIG. 33(A), FIG. 33(B), FIG. 33(C), and FIG. 33(D) and a flow chartin FIG. 33(E).

First, a lattice point group was extracted by the method shown in FIG.32 and the like (see FIG. 33(A) and Step S111 in FIG. 33(E)). Next,adjacent lattice points were connected with segments (see FIG. 33(B) andStep S112 in FIG. 33(E)). Then, perpendicular bisectors of the segmentswere drawn (see FIG. 33(C) and Step S113 in FIG. 33(E)). Subsequently,points where three perpendicular bisectors intersect were extracted (seeStep S114 in FIG. 33(E)). The points are called Voronoi points. Afterthat, adjacent Voronoi points were connected with segments (see FIG.33(D) and Step S115 in FIG. 33(E)). A polygonal region surrounded by thesegments at this point is called a Voronoi region. In the above method,a Voronoi diagram was formed.

FIG. 34 shows the proportions of the shapes of Voronoi regions (any oftetragon to enneagon) in Sample 1A, Sample 1C, Sample 1D, Sample 1F,Sample 1G, and Sample 1J. Bar graphs show the numbers of the shapes ofVoronoi regions (any of tetragon to enneagon) in the samples.Furthermore, tables show the proportions of the shapes of Voronoiregions (any of tetragon to enneagon) in the samples.

It was found from FIG. 34 that the proportion of hexagons was likely tobe high in Sample 1J with a high degree of crystallinity and theproportion of hexagons was likely to be low in Sample 1A with a lowdegree of crystallinity. The proportion of hexagons in Sample 1D wasbetween that in Sample 1J and that of Sample 1A. Accordingly, it wasfound from FIG. 34 that the crystal state of the metal oxidesignificantly differs under different formation conditions.

It was found from FIG. 34 that as the substrate temperature at the timeof film formation is lower or the oxygen gas flow rate ratio at the timeof film formation is lower, the degree of crystallinity is lower and theproportion of hexagons is lower.

<Elementary Analysis>

This section describes the analysis results of elements included inSample 1A. For the analysis, by energy dispersive X-ray spectroscopy(EDX), EDX mapping images are obtained and evaluated. An energydispersive X-ray spectrometer Analysis Station JED-2300T manufactured byJEOL Ltd. is used as an elementary analysis apparatus in the EDXmeasurement. A Si drift detector is used to detect an X-ray emitted fromthe sample.

In the EDX measurement, an EDX spectrum of a point is obtained in such amanner that electron beam irradiation is performed on the point in adetection target region of a sample, and the energy of characteristicX-ray of the sample generated by the irradiation and its frequency aremeasured. In this example, peaks of an EDX spectrum of the point areattributed to electron transition to the L shell in an In atom, electrontransition to the K shell in a Ga atom, and electron transition to the Kshell in a Zn atom and the K shell in an O atom, and the proportions ofthe atoms in the point are calculated. An EDX mapping image indicatingdistributions of proportions of atoms can be obtained through theprocess in an analysis target region of a sample.

FIG. 35 shows a cross-sectional TEM image, a plan-view TEM image, andEDX mapping images of Sample 1A. In the EDX mapping images, theproportion of an element is indicated by grayscale: the more measuredelements exist in a region, the brighter the region is; the lessmeasured elements exist in a region, the darker the region is. Themagnification of the EDX mapping images in FIG. 35 is 7,200,000 times.

FIG. 35(A) shows a cross-sectional TEM image, and FIG. 35(E) shows aplan-view TEM image. FIG. 35(B) shows a cross-sectional EDX mappingimage of In atoms, and FIG. 35(F) shows a plan-view EDX mapping image ofIn atoms. In the EDX mapping image in FIG. 35(B), the proportion of theIn atoms in all the atoms is the range of 9.28 to 33.74 [atomic %]. Inthe EDX mapping image in FIG. 35(F), the proportion of the In atoms inall the atoms is in the range of 12.97 to 38.01 [atomic %].

FIG. 35(C) shows a cross-sectional EDX mapping image of Ga atoms, andFIG. 35(G) shows a plan-view EDX mapping image of Ga atoms. In the EDXmapping image in FIG. 35(C), the proportion of the Ga atoms in all theatoms is in the range of 1.18 to 18.64 [atomic %]. In the EDX mappingimage in FIG. 35(G), the proportion of the Ga atoms in all the atoms isin the range of 1.72 to 19.82 [atomic %].

FIG. 35(D) shows a cross-sectional EDX mapping image of Zn atoms, andFIG. 35(H) shows a plan-view EDX mapping image of Zn atoms. In the EDXmapping image in FIG. 35(D), the proportion of the Zn atoms in all theatoms is in the range of 6.69 to 24.99 [atomic %]. In the EDX mappingimage in FIG. 35(H), the proportion of the Zn atoms in all the atoms isin the range of 9.29 to 28.32 [atomic %].

Note that FIG. 35(A), FIG. 35(B), FIG. 35(C), and FIG. 35(D) show thesame region in the cross section of Sample 1A. FIG. 35(E), FIG. 35(F),FIG. 35(G), and FIG. 35(H) show the same region in the plane of Sample1A.

FIG. 36 shows enlarged cross-sectional EDX mapping images and enlargedplan-view EDX mapping images of Sample 1A. FIG. 36(A) is an enlargedview of a part in FIG. 35(B). FIG. 36(B) is an enlarged view of a partin FIG. 35(C). FIG. 36(C) is an enlarged view of a part in FIG. 35(D).FIG. 36(D) is an enlarged view of a part in FIG. 35(F). FIG. 36(E) is anenlarged view of a part in FIG. 35(G). FIG. 36(F) is an enlarged view ofa part in FIG. 35(H).

The EDX mapping images in FIG. 36(A), FIG. 36(B), and FIG. 36(C) showrelative distribution of bright and dark areas, indicating that theatoms have distributions in Sample 1A. Areas surrounded by solid linesand areas surrounded by dashed lines in FIG. 36(A), FIG. 36(B), and FIG.36(C) were focused on.

As shown in FIG. 36(A), a relatively bright region occupies a large areain the area surrounded by the solid line and a relatively dark regionoccupies a large area in the area surrounded by the dashed line. Asshown in FIG. 36(B), a relatively dark region occupies a large area inthe area surrounded by the solid line and a relatively bright regionoccupies a large area in the area surrounded by the dashed line.

That is, it was found that the areas surrounded by the solid lines wereregions including a relatively large number of In atoms and the areassurrounded by the dashed lines were regions including a relatively smallnumber of In atoms. FIG. 36(C) shows that a lower portion of the areasurrounded by the solid line is relatively bright and an upper portionthereof is relatively dark. Thus, it was found that the area surroundedby the solid line was a region including In_(X2)Zn_(Y2)O_(Z2), InO_(X1),or the like as a main component.

It was also found that the area surrounded by the solid line was aregion including a relatively small number of Ga atoms and the areasurrounded by the dashed line was a region including a relatively largenumber of Ga atoms. FIG. 36(C) shows that a left portion of the areasurrounded by the dashed line is relatively dark and a right portionthereof is relatively bright. Thus, it was found that the areasurrounded by the dashed line was a region including GaO_(X3),Ga_(X4)Zn_(Y4)O_(Z4), or the like as a main component.

Similarly, areas surrounded by solid lines and dashed lines in the EDXmapping images in FIG. 36(D), FIG. 36(E), and FIG. 36(F) are focused on.

As shown in FIG. 36(D), a relatively bright region occupies a large areain the area surrounded by the solid line and a relatively dark regionoccupies a large area in the area surrounded by the dashed line. Asshown in FIG. 36(E), a relatively dark region occupies a large area inthe area surrounded by the solid line and a relatively bright regionoccupies a large area in the area surrounded by the dashed line.

That is, it was found that the areas surrounded by the solid lines wereregions including a relatively large number of In atoms and a relativelysmall number of Ga atoms. FIG. 36(F) shows that a lower portion of thearea surrounded by the solid line is relatively dark and an upperportion thereof is relatively bright. Thus, it was found that the areasurrounded by the solid line was a region includingIn_(X2)Zn_(Y2)O_(Z2), InO_(X1), or the like as a main component.

It was also found that the area surrounded by the dashed line was aregion including a relatively small number of In atoms and a regionincluding a relatively large number of Ga atoms. FIG. 36(F) shows that aright portion of the area surrounded by the dashed line is relativelydark and a left portion thereof is relatively bright. Thus, it was foundthat the area surrounded by the dashed line was a region includingGaO_(X3), Ga_(X4)Zn_(Y4)O_(Z4), or the like as a main component.

Furthermore, as shown in FIG. 36 , the In atoms are relatively moreuniformly distributed than the Ga atoms, and regions including InO_(X1)as a main component are seemingly joined to each other through a regionincluding In_(X2)Zn_(Y2)O_(Z2) as a main component. It can be thuspresumed that the regions including In_(X2)Zn_(Y2)O_(Z2) or InO_(X1) asa main component extend like a cloud.

An In—Ga—Zn oxide having a composition in which the regions includingGaO_(X3) as a main component and the regions includingIn_(X2)Zn_(Y2)O_(Z2) or InO_(X1) as a main component are unevenlydistributed and mixed can be referred to as CAC-IGZO.

In FIG. 36 , each of the regions including GaO_(X3) as a main componentand the regions including In_(X2)Zn_(Y2)O_(Z2) or InO_(X1) as a maincomponent was observed to have a size greater than or equal to 0.5 nmand less than or equal to 10 nm, or greater than or equal to 1 nm andless than or equal to 3 nm.

As described above, it was confirmed that the CAC-IGZO has a structuredifferent from that of an IGZO compound in which metal elements areevenly distributed, and has characteristics different from those of theIGZO compound. That is, it was confirmed that in the CAC-IGZO, regionsincluding GaO_(X3) or the like as a main component and regions includingIn_(X2)Zn_(Y2)O_(Z2) or InO_(X1) as a main component were separated toform a mosaic pattern.

Accordingly, it can be expected that when CAC-IGZO is used for asemiconductor element, the property derived from GaO_(X3) or the likeand the property derived from In_(X2)Zn_(Y2)O_(Z2) or InO_(X1)complement each other, whereby high on-state current (I_(on)), highfield-effect mobility (μ), and low off-state current (I_(off)) can beachieved. A semiconductor element including CAC-IGZO has highreliability. Thus, CAC-IGZO is suitably used in a variety ofsemiconductor devices typified by a display.

At least part of this example can be implemented in combination with anyof the embodiments and the other examples described in thisspecification as appropriate.

Example 2

In this example, the transistor 150 including the metal oxide 108 of oneembodiment of the present invention was fabricated and subjected totests for electrical characteristics and reliability. In this example,nine transistors, i.e., Sample 2A, Sample 2B, Sample 2C, Sample 2D,Sample 2E, Sample 2F, Sample 2G, Sample 2H, and Sample 2J, werefabricated as the transistor 150 including the metal oxide 108.

<Structure of Samples and Fabrication Method Thereof

Sample 2A, Sample 2B, Sample 2C, Sample 2D, Sample 2E, Sample 2F, Sample2G, Sample 2H, and Sample 2J relating to one embodiment of the presentinvention will be described below. As Sample 2A to Sample 2J, thetransistors 150 having the structure illustrated in FIG. 7 werefabricated by the fabrication method described in Embodiment 2 withreference to FIG. 9 to FIG. 11 .

Sample 2A to Sample 2J were fabricated at different temperatures anddifferent oxygen flow rate ratios in film formation of the metal oxide108. The temperatures and the oxygen flow rate ratios in film formationof the metal oxides of Sample 2A to Sample 2J are shown in the followingtable.

TABLE 3 Formation condition of metal oxide 108 O₂ Formation Flow rate[sccm] ratio temperature O₂ Ar [%] [° C.] Sample 2A 30 270 10 R.T.Sample 2B 90 210 30 R.T. Sample 2C 300 0 100 R.T. Sample 2D 30 270 10130 Sample 2E 90 210 30 130 Sample 2F 300 0 100 130 Sample 2G 30 270 10170 Sample 2H 90 210 30 170 Sample 2J 300 0 100 170

The samples were fabricated by the fabrication method described inEmbodiment 2. The metal oxide 108 was formed using a metal oxide target(In:Ga:Zn=4:2:4.1 [atomic ratio]).

The transistor 150 had a channel length of 2 μm and a channel width of 3μm (hereinafter, also referred to as L/W=2/3 μm) or a channel length of2 μm and a channel width of 50 μm (hereinafter, also referred to asL/W=2/50 μm).

<Electrical Characteristics of Transistors>

Next, I_(d)-V_(g) characteristics of the transistors (L/W=2/3 μm) inSample 2A to Sample 2J fabricated above were measured. As conditions formeasuring the I_(d)-V_(g) characteristics of each transistor, a voltageapplied to the conductive film 112 serving as a first gate electrode(hereinafter, the voltage is also referred to as gate voltage (V_(g)))and a voltage applied to the conductive film 106 serving as a secondgate electrode (hereinafter, the voltage is also referred to as backgate voltage (V_(bg))) were changed from −10 V to +10 V in increments of0.25 V. A voltage applied to the conductive film 120 a serving as asource electrode (the voltage is also referred to as source voltage(V_(s))) was 0 V (comm), and a voltage applied to the conductive film120 b serving as a drain electrode (the voltage is also referred to asdrain voltage (V_(d))) was 0.1 V and 20 V.

[I_(d)-V_(g) Characteristics of Transistor]

Here, drain current-gate voltage characteristics (I_(d)-V_(g)characteristics) of a transistor are described. FIG. 39(A) illustratesan example of I_(d)-V_(g) characteristics of the transistor. FIG. 39(A)shows the case where polycrystalline silicon is used for an active layerof the transistor for easy understanding. In FIG. 39(A), the verticalaxis and the horizontal axis represent I_(d) (Drain Current) and V_(g)(Gate Voltage), respectively.

As shown in FIG. 39(A), I_(d)-V_(g) characteristics are broadly dividedinto three regions. A first region, a second region, and a third regionare referred to as an off region (OFF region), a subthreshold region,and an on region (ON region), respectively. A gate voltage at a boundarybetween the subthreshold region and the on region is referred to as athreshold voltage (V_(th)).

To obtain favorable characteristics of the transistor, it is preferablethat the drain current in the off region (also referred to as off-statecurrent or I_(off)) be low and the drain current in the on region (alsoreferred to as on-state current or I_(on)) be high. As an index of theon-state current of the transistor, the field-effect mobility is oftenused. The details of the field-effect mobility will be described later.

To drive the transistor at a low voltage, the slope of the I_(d)-V_(g)characteristics in the subthreshold region is preferably steep. An indexof the degree of change in the I_(d)-V_(g) characteristics in thesubthreshold region is referred to as subthreshold swing (SS) or an Svalue. The S value is represented by the following formula (2).

$\begin{matrix}\left\lbrack {{Formula}2} \right\rbrack &  \\{{SS} = {\min\left( \frac{\partial V_{g}}{\partial{\log_{10}\left( I_{d} \right)}} \right)}} & (2)\end{matrix}$

The S value is a minimum value of the amount of change in gate voltagewhich is needed for changing a drain current by an order of magnitude inthe subthreshold region. As the S value is smaller, switching operationbetween on and off states can be performed rapidly.

[I_(d)-V_(d) Characteristics of Transistor]

Next, drain current-drain voltage characteristics (I_(d)-V_(d)characteristics) of a transistor are described. FIG. 39(B) shows anexample of I_(d)-V_(d) characteristics of the transistor. In FIG. 39(B),the vertical axis and the horizontal axis represent I_(d) and V_(d),respectively.

As illustrated in FIG. 39(B), the on region is further divided into tworegions. A first region and a second region are referred to as a linearregion and a saturation region, respectively. In the linear region,drain current increases in a parabola shape in accordance with theincrease in drain voltage. On the other hand, in the saturation region,drain current does not greatly change even when drain voltage changes.According to a vacuum tube, the linear region and the saturation regionare referred to as a triode region and a pentode region, respectively,in some cases.

The linear region indicates the state where V_(g) is higher than V_(d)(V_(d)<V_(g)) in some cases. The saturation region indicates the statewhere V_(d) is higher than V_(g) (V_(g)<V_(d)) in some cases. However,in practice, the threshold voltage of the transistor needs to beconsidered. Thus, the state where a value obtained by subtracting thethreshold voltage of the transistor from V_(g) is higher than V_(d)(V_(d)<V_(g)−V_(th)) is referred to as the linear region in some cases.Similarly, the state where a value obtained by subtracting the thresholdvoltage of the transistor from V_(g) is lower than V_(d)(V_(g)−V_(th)<V_(d)) is referred to as the saturation region in somecases.

The I_(d)-V_(a) characteristics of the transistor with which current inthe saturation region is constant are expressed as “favorablesaturation” in some cases. The favorable saturation of the transistor isimportant particularly when the transistor is used in an organic ELdisplay. For example, the use of a transistor with favorable saturationas a transistor of a pixel of an organic EL display can suppress achange in luminance of the pixel even when the drain voltage is changed.

[Analysis Model of Drain Current]

Next, an analysis model of the drain current is described. As theanalysis model of the drain current, analytic formulae of drain currentbased on gradual channel approximation (GCA) is known. On the basis ofGCA, the drain current of the transistor is represented by the followingformula (3).

$\begin{matrix}\left\lbrack {{Formula}3} \right\rbrack &  \\{I_{d} = \left\{ \begin{matrix}{\mu\frac{W}{L}{C_{OX}\left\lbrack {{\left( {{Vg} - V_{th}} \right)V_{d}} - {\frac{1}{2}V_{d}^{2}}} \right\rbrack}\ldots\left( {{V_{g} - V_{th}} > V_{d}} \right)} \\{\mu\frac{W}{2L}{C_{OX}\left( {{Vg} - V_{th}} \right)}^{2}\ldots\ \left( {{V_{g} - V_{th}} \leq V_{d}} \right)}\end{matrix} \right.} & (3)\end{matrix}$

In the formula (3), the upper formula is a formula for drain current ina linear region and the lower formula is a formula for drain current ina saturation region. In the formula (3), I_(d) represents the draincurrent, μ represents the mobility of the active layer, L represents thechannel length of the transistor, W represents the channel width of thetransistor, Cox represents the gate capacitance, V_(g) represents thegate voltage, V_(d) represents the drain voltage, and V_(th) representsthe threshold voltage of the transistor.

[Field-Effect Mobility]

Next, field-effect mobility is described. As an index of current drivecapability of a transistor, the field-effect mobility is used. Asdescribed above, the on region of the transistor is divided into thelinear region and the saturation region. From the characteristics in theregions, the field-effect mobility of the transistor can be calculatedon the basis of the analytic formulae of the drain current based on GCA.The field-effect mobility in the linear region and the field-effectmobility in the saturation region are referred to as linear mobility andsaturation mobility, respectively, when they need to be distinguishedfrom each other. The linear mobility is represented by the followingformula (4) and the saturation mobility is represented by the followingformula (5).

$\begin{matrix}\left\lbrack {{Formula}4} \right\rbrack &  \\{\mu_{FE}^{lin} = {\frac{L}{WC_{OX}}\frac{\partial I_{d}}{\partial V_{g}}\frac{1}{V_{d}}}} & (4)\end{matrix}$ $\begin{matrix}\left\lbrack {{Formula}5} \right\rbrack &  \\{\mu_{FE}^{sat} = {\frac{2L}{WC_{OX}}\left( \frac{\partial\sqrt{I_{d}}}{\partial V_{g}} \right)^{2}}} & (5)\end{matrix}$

In this specification and the like, curves calculated from the formula(4) and the formula (5) are referred to as mobility curves. FIG. 40shows mobility curves calculated from the analytic formulae of draincurrent based on GCA. In FIG. 40 , the I_(d)-V_(g) characteristics atV_(d)=10 V and the mobility curves of the linear mobility and thesaturation mobility at the time when GCA is assumed to be effective areshown together (the value of mobility corresponds to the Field-effectivemobility on the right vertical axis).

In FIG. 40 , the I_(d)-V_(g) characteristics are calculated from theanalytic formulae of drain current based on GCA. The shapes of themobility curves can be a lead to understanding the state of the insideof the transistor.

FIG. 37 shows the results of I_(d)-V_(g) characteristics andfield-effect mobilities of Sample 2A to Sample 2J. The solid line andthe dashed-dotted line represent I_(d) at V_(d)=20 V and I_(d) atV_(d)=0.1 V, respectively. The dashed line represents field-effectmobility. In FIG. 37 , the first vertical axis represents I_(d) [A], thesecond vertical axis represents field-effect mobility (μFE) [cm²/Vs],and the horizontal axis represents V_(g) [V]. The field-effect mobilitywas calculated from the value measured at V_(g)=20 V.

As shown in FIG. 37 , it was found that Sample 2A to Sample 2J havedifferent on-state currents (I_(on)) and different field-effectmobilities, particularly different field-effect mobilities in saturationregions. In particular, the maximum saturation mobilities and the risingcharacteristics of the field-effect mobilities around 0 V were found todiffer distinctly.

It was found from FIG. 37 that as the substrate temperature at the timeof film formation is lower or the oxygen flow rate ratio at the time offilm formation is lower, the on-state current (I_(on)) becomes higher.It was also found that the field-effect mobility rises more steeplyaround 0 V. In particular, Sample 2A was found to have a maximumfield-effect mobility close to 70 cm²/Vs.

<Gate Bias-Temperature Stress Test (GBT Test)>

Next, the reliability of the above transistors (L/W=2/50 μm) of Sample2A to Sample 2J was evaluated. As the reliability evaluation, GBT testswere used.

The conditions for GBT tests in this example were as follows. A voltageapplied to the conductive film 112 serving as the first gate electrodeand the conductive film 106 serving as the second gate electrode(hereinafter referred to as gate voltage (V_(g))) was ±30 V, and avoltage applied to a conductive film functioning as the conductive film120 a serving as the source electrode and the conductive film 120 bserving as a drain electrode (hereinafter referred to as source voltage(V_(s)) and drain voltage (V_(d)), respectively) was 0 V (COMMON). Thestress temperature was 60° C., the time for stress application was 1hour, and two kinds of measurement environments, a dark environment anda photo environment (irradiation with light at approximately 10,000 lxfrom a white LED), were employed.

In other words, the conductive film 120 a serving as the sourceelectrode of the transistor 150 and the conductive film 120 b serving asthe drain electrode of the transistor 150 were set at the samepotential, and a potential different from that of the conductive film120 a serving as the source electrode and the conductive film 120 bserving as the drain electrode was applied to the conductive film 112serving as the first gate electrode and the conductive film 106 servingas the second gate electrode for a certain time (here, one hour).

A case where the potential applied to the conductive film 112 serving asthe first gate electrode and the conductive film 106 serving as thesecond gate electrode is higher than the potential applied to theconductive film 120 a serving as the source electrode and the conductivefilm 120 b serving as the drain electrode is called positive stress. Acase where the potential applied to the conductive film 112 serving asthe first gate electrode and the conductive film 106 serving as thesecond gate electrode is lower than the potential applied to theconductive film 120 a serving as the source electrode and the conductivefilm 120 b serving as the drain electrode is called negative stress.Thus, the reliability evaluation was performed under four conditions intotal, i.e., positive GBT (dark), negative GBT (dark), positive GBT(light irradiation), and negative GBT (light irradiation).

Note that in the following description, the positive GBT (dark) isreferred to as positive bias temperature stress (PBTS). The negative GBT(dark) is referred to as negative bias temperature stress (NBTS). Thepositive GBT (light irradiation) is referred to as positive biasillumination temperature stress (PBITS). The negative GBT (lightirradiation) is referred to as negative bias illumination temperaturestress (NBITS).

FIG. 38 shows the GBT test results of Sample 2A to Sample 2J. In FIG. 38, the vertical axis represents the amount of shift in the thresholdvoltage (ΔV_(th)) of the transistors.

The results in FIG. 38 indicate that the amount of shift in thethreshold voltage (ΔV_(th)) of each of the transistors included inSample 2A to Sample 2J was within ±3 V in the GBT tests. Thus, it isconfirmed that the transistors included in Sample 2A to Sample 2J eachhave high reliability.

Thus, even the IGZO film having low crystallinity is presumed to have alow density of defect states like an IGZO film having highcrystallinity.

At least part of this example can be implemented in combination with anyof the embodiments and the other examples described in thisspecification as appropriate.

Example 3

In this example, a metal oxide of one embodiment of the presentinvention, which was formed over a substrate, was measured with avariety of methods, and the measurement results are described. Note thatin this example, Sample 3A, Sample 3D, and Sample 3J were fabricated.

<Structure of Samples and Fabrication Method Thereof>

Sample 3A, Sample 3D, and Sample 3J relating to one embodiment of thepresent invention are described below. Sample 3A, Sample 3D, and Sample3J each include a substrate and a metal oxide over the substrate.

Sample 3A, Sample 3D, and Sample 3J were fabricated at differenttemperatures and different oxygen flow rate ratios in film formation ofthe metal oxide. The temperatures and the oxygen flow rate ratios infilm formation of the metal oxides of Sample 3A, Sample 3D, and Sample3J are shown in the following table.

TABLE 4 O₂ Formation Flow rate [sccm] ratio temperature O₂ Ar [%] [° C.]Sample 3A 30 270 10 R.T. Sample 3D 30 270 10 130 Sample 3J 150 150 50170

Next, methods for fabricating the samples will be described.

A glass substrate was used as the substrate. Over the substrate, a100-nm-thick In—Ga—Zn metal oxide was formed as a metal oxide with asputtering apparatus. The formation conditions were as follows: thepressure in a chamber was 0.6 Pa; and a metal oxide target (an atomicratio of In:Ga:Zn=1:1:1.2) was used as a target. The metal oxide targetprovided in the sputtering apparatus was supplied with an AC power of2500 W, so that the metal oxide film was formed.

The formation temperatures and oxygen flow rate ratios shown in theabove table were used as the conditions for forming metal oxide films tofabricate Sample 3A, Sample 3D, and Sample 3J.

Through the above steps, Sample 3A, Sample 3D, and Sample 3J in thisexample were fabricated.

<TEM Images and Electron Diffraction>

This section describes the TEM observation and analysis results ofSample 3A, Sample 3D, and Sample 3J.

This section also describes electron diffraction patterns obtained byirradiation of Sample 3A, Sample 3D, and Sample 3J with an electron beamwith a probe diameter of 1 nm (also referred to as a nanobeam electronbeam).

The plan-view TEM images were observed with a spherical aberrationcorrector function. The HAADF-STEM images were obtained using an atomicresolution analytical electron microscope JEM-ARM200F manufactured byJEOL Ltd. under the following conditions: the acceleration voltage was200 kV; and irradiation with an electron beam with a diameter ofapproximately 0.1 nmφ was performed.

Note that the electron diffraction patterns were observed while anelectron beam irradiation was performed at a constant rate from 0 secondto 35 seconds.

FIG. 41(A) shows a cross-sectional TEM image of Sample 3A, and FIG.41(B) shows an electron diffraction pattern of Sample 3A. FIG. 41(C)shows a cross-sectional TEM image of Sample 3D, and FIG. 41(D) shows anelectron diffraction pattern of Sample 3D. FIG. 41(E) shows across-sectional TEM image of Sample 3J, and FIG. 41(F) shows an electrondiffraction pattern of Sample 3J.

A nanocrystal was found in Sample 3A from the result of thecross-sectional TEM observation as shown in FIG. 41(A). As shown in FIG.41(B), the observed electron diffraction pattern of Sample 3A has aregion with high luminance in a circular (ring) pattern. Furthermore, aplurality of spots were observed in the ring-shaped region.

Sample 3D was found to have a CAAC structure and a nanocrystal from theresult of the cross-sectional TEM observation shown in FIG. 41(C). Asshown in FIG. 41(D), the observed electron diffraction pattern of Sample3D has a region with high luminance in a circular (ring) pattern.Furthermore, a plurality of spots were observed in the ring-shapedregion. In the diffraction pattern, spots derived from the (009) planewere slightly observed.

Meanwhile, Sample 3J was clearly found to have layered arrangement of aCAAC structure from the result of the cross-sectional TEM observation inFIG. 41(E). Furthermore, spots derived from the (009) plane were foundin the result of the electron diffraction pattern of Sample 3J shown inFIG. 41(F).

The features observed in the cross-sectional TEM images and theplan-view TEM images are one aspect of a structure of a metal oxide.

As described above, the electron diffraction patterns of Sample 3A andSample 3D each have a region with high luminance in a ring pattern and aplurality of bright spots appear in the ring-shaped region. It was thusfound that Sample 3A and Sample 3D exhibit an electron diffractionpattern of the metal oxide including nanocrystals and do not showalignment in the plane direction and the cross-sectional direction.Sample 3D was found to be a mixed material of the nc structure and theCAAC structure.

Meanwhile, the electron diffraction pattern of Sample 3J includes spotsderived from the (009) plane of an InGaZnO₄ crystal. It was thus foundthat Sample 3J had c-axis alignment and the c-axes were aligned in thedirection substantially perpendicular to the formation surface or thetop surface of Sample 3J.

<Analysis of TEM Image>

This section describes the observation and analysis results of Sample3A, Sample 3D, and Sample 3J with an HAADF-STEM.

The results of image analysis of plan-view TEM images are described. Theplan-view TEM images were obtained with a spherical aberration correctorfunction. The plan-view TEM images were obtained using an atomicresolution analytical electron microscope JEM-ARM200F manufactured byJEOL Ltd. under the following conditions: the acceleration voltage was200 kV; and irradiation with an electron beam with a diameter ofapproximately 0.1 nmφ was performed.

FIG. 42(A) shows a plan-view TEM image of Sample 3A, and FIG. 42(B)shows an image obtained through image processing of the plan-view TEMimage of Sample 3A. FIG. 42(C) shows a plan-view TEM image of Sample 3Dand FIG. 42(D) shows an image obtained through image processing of theplan-view TEM image of Sample 3D. FIG. 42(E) shows a plan-view TEM imageof Sample 3J and FIG. 42(F) shows an image obtained through imageprocessing of the plan-view TEM image of Sample 3J.

The images obtained through image processing was then shown in such amanner that color or gradation changes in accordance with the angle ofthe hexagonal lattice in the region. The images obtained through imageprocessing of the plan-view TEM images in FIG. 42(B), FIG. 42(D), andFIG. 42(F) are images obtained by performing image analysis on theplan-view TEM images in FIG. 42(A), FIG. 42(C), and FIG. 42(E) by themethod described in Example 1 and applying gradation in accordance withthe angle of the hexagonal lattice. In other words, the images obtainedthrough the image processing of the plan-view TEM images are images inwhich the orientations of lattice points in certain wavenumber rangesare extracted by color-coding the certain wavenumber ranges in an FFTfiltering image of the plan-view TEM image.

As shown in FIG. 42 , in Sample 3A and Sample 3D in which nc wasobserved, the hexagons were oriented randomly and distributed in amosaic pattern. In Sample 3J in which a layered structure was observedin the cross-sectional TEM image, regions with uniformly orientedhexagons exist in a large area of several tens of nanometers. It wasfound that Sample 3D included an nc region in a random mosaic patternand a large-area region with uniform orientation as in Sample 3J.

It was found from FIG. 42 that as the substrate temperature at the timeof film formation is lower or the oxygen gas flow rate ratio at the timeof film formation is lower, regions in which the hexagons are orientedrandomly and distributed in a mosaic pattern are likely to exist.

Through the analysis of a plan-view TEM image of a CAAC-OS, a boundaryportion where angles of hexagonal lattices change can be examined.

Next, Voronoi diagrams were formed using lattice point groups in Sample3A. The Voronoi diagrams were obtained by the method described inExample 1.

FIG. 43(A), FIG. 43(B), and FIG. 43(C) show the proportions of theshapes of Voronoi regions (any of tetragon to enneagon) in Sample 3A,Sample 3D, and Sample 3J, respectively. Bar graphs show the numbers ofthe shapes of Voronoi regions (any of tetragon to enneagon) in thesamples. Furthermore, tables show the proportions of the shapes ofVoronoi regions (any of tetragon to enneagon) in the samples.

It was found from FIG. 43 that the proportion of hexagons was likely tobe high in Sample 3J with a high degree of crystallinity and theproportion of hexagons was likely to be low in Sample 3A with a lowdegree of crystallinity. The proportion of hexagons in Sample 3D wasbetween that in Sample 3J and that of Sample 3A. Accordingly, it wasfound from FIG. 43 that the crystal state of the metal oxidesignificantly differs under different formation conditions.

It was found from FIG. 43 that as the substrate temperature at the timeof film formation is lower or the oxygen gas flow rate ratio at the timeof film formation is lower, the degree of crystallinity is lower and theproportion of hexagons is lower.

<Elementary Analysis>

This section describes the analysis results of elements included inSample 3A. For the analysis, by energy dispersive X-ray spectroscopy(EDX), EDX mapping images are obtained and evaluated. An energydispersive X-ray spectrometer Analysis Station JED-2300T manufactured byJEOL Ltd. is used as an elementary analysis apparatus in the EDXmeasurement. A Si drift detector is used to detect an X-ray emitted fromthe sample.

In the EDX measurement, an EDX spectrum of a point is obtained in such amanner that electron beam irradiation is performed on the point in adetection target region of a sample, and the energy of characteristicX-ray of the sample generated by the irradiation and its frequency aremeasured. In this example, peaks of an EDX spectrum of the point areattributed to electron transition to the L shell in an In atom, electrontransition to the K shell in a Ga atom, and electron transition to the Kshell in a Zn atom and the K shell in an O atom, and the proportions ofthe atoms in the point are calculated. An EDX mapping image indicatingdistributions of proportions of atoms can be obtained through theprocess in an analysis target region of a sample.

FIG. 44 shows a cross-sectional TEM image, a plan-view TEM image, andEDX mapping images of Sample 3A. In the EDX mapping images, theproportion of an element is indicated by grayscale: the more measuredelements exist in a region, the brighter the region is; the lessmeasured elements exist in a region, the darker the region is. Themagnification of the EDX mapping images in FIG. 44 is 7,200,000 times.

FIG. 44(A) shows a cross-sectional TEM image, and FIG. 44(E) shows aplan-view TEM image. FIG. 44(B) shows a cross-sectional EDX mappingimage of In atoms, and FIG. 44(F) shows a plan-view EDX mapping image ofIn atoms. In the EDX mapping image in FIG. 44(B), the proportion of theIn atoms in all the atoms is the range of 8.64 to 34.91 [atomic %]. Inthe EDX mapping image in FIG. 44(F), the proportion of the In atoms inall the atoms is in the range of 5.76 to 34.69 [atomic %].

FIG. 44(C) shows a cross-sectional EDX mapping image of Ga atoms, andFIG. 44(G) shows a plan-view EDX mapping image of Ga atoms. In the EDXmapping image in FIG. 44(C), the proportion of the Ga atoms in all theatoms is in the range of 2.45 to 25.22 [atomic %]. In the EDX mappingimage in FIG. 44(G), the proportion of the Ga atoms in all the atoms isin the range of 1.29 to 27.64 [atomic %].

FIG. 44(D) shows a cross-sectional EDX mapping image of Zn atoms, andFIG. 44(H) shows a plan-view EDX mapping image of Zn atoms. In the EDXmapping image in FIG. 44(D), the proportion of the Zn atoms in all theatoms is in the range of 5.05 to 23.47 [atomic %]. In the EDX mappingimage in FIG. 44(H), the proportion of the Zn atoms in all the atoms isin the range of 3.69 to 27.86 [atomic %].

Note that FIG. 44(A), FIG. 44(B), FIG. 44(C), and FIG. 44(D) show thesame region in the cross section of Sample 3A. FIG. 44(E), FIG. 44(F),FIG. 44(G), and FIG. 44(H) show the same region in the plane of Sample3A.

FIG. 45 shows enlarged cross-sectional EDX mapping images of Sample 3A.FIG. 45(A) is an enlarged view of a part in FIG. 44(B). FIG. 45(B) is anenlarged view of a part in FIG. 44(C). FIG. 45(C) is an enlarged view ofa part in FIG. 44(D).

The EDX mapping images in FIG. 45(A), FIG. 45(B), and FIG. 45(C) showrelative distribution of bright and dark areas, indicating that theatoms have distributions in Sample 3A. Areas surrounded by solid linesand areas surrounded by dashed lines in FIG. 45(A), FIG. 45(B), and FIG.45(C) were focused on.

As shown in FIG. 45(A), a relatively dark region occupies a large areain the area surrounded by the solid line and a relatively bright regionoccupies a large area in the area surrounded by the dashed line. Asshown in FIG. 45(B), a relatively bright region occupies a large area inthe area surrounded by the solid line and a relatively dark regionoccupies a large area in the area surrounded by the dashed line.

That is, it was found that the areas surrounded by the solid lines wereregions including a relatively large number of In atoms and the areassurrounded by the dashed lines were regions including a relatively smallnumber of In atoms. FIG. 45(C) shows that an upper portion of the areasurrounded by the solid line is relatively bright and a lower portionthereof is relatively dark. Thus, it was found that the area surroundedby the solid line was a region including In_(X2)Zn_(Y2)O_(Z2), InO_(X1),or the like as a main component.

It was also found that the area surrounded by the solid line was aregion including a relatively small number of Ga atoms and the areasurrounded by the dashed line was a region including a relatively largenumber of Ga atoms. FIG. 45(C) shows that a right portion of the areasurrounded by the upper dashed line is relatively bright and a leftportion thereof is relatively dark. FIG. 45(C) also shows that an upperleft portion of the area surrounded by the lower dashed line isrelatively bright and a lower right portion thereof is relatively dark.Thus, it was found that the area surrounded by the dashed line was aregion including GaO_(X3), Ga_(X4)Zn_(Y4)O_(Z4), or the like as a maincomponent.

Furthermore, as shown in FIG. 45(A), FIG. 45(B), and FIG. 45(C), the Inatoms are relatively more uniformly distributed than the Ga atoms, andregions including InO_(X1) as a main component are seemingly joined toeach other through a region including In_(X2)Zn_(Y2)O_(Z2) as a maincomponent. It can be thus presumed that the regions includingIn_(X2)Zn_(Y2)O_(Z2) or InO_(X1) as a main component extend like acloud.

An In—Ga—Zn oxide having a composition in which the regions includingGaO_(X3) as a main component and the regions includingIn_(X2)Zn_(Y2)O_(Z2) or InO_(X1) as a main component are unevenlydistributed and mixed can be referred to as CAC-IGZO.

In FIG. 45(A), FIG. 45(B), and FIG. 45(C), each of the regions includingGaO_(X3) as a main component and the regions includingIn_(X2)Zn_(Y2)O_(Z2) or InO_(X1) as a main component was observed tohave a size greater than or equal to 0.5 nm and less than or equal to 10nm, or greater than or equal to 1 nm and less than or equal to 3 nm.

FIG. 46 shows a cross-sectional TEM image, a plan-view TEM image, andEDX mapping images of Sample 3J. In the EDX mapping images, theproportion of an element is indicated by grayscale: the more measuredelements exist in a region, the brighter the region is; the lessmeasured elements exist in a region, the darker the region is. Themagnification of the EDX mapping images in FIG. 46 is 7,200,000 times.

FIG. 46(A) shows a cross-sectional TEM image, and FIG. 46(E) shows aplan-view TEM image. FIG. 46(B) shows a cross-sectional EDX mappingimage of In atoms, and FIG. 46(F) shows a plan-view EDX mapping image ofIn atoms. In the EDX mapping image in FIG. 46(B), the proportion of theIn atoms in all the atoms is the range of 9.70 to 40.47 [atomic %]. Inthe EDX mapping image in FIG. 46(F), the proportion of the In atoms inall the atoms is in the range of 9.16 to 35.76 [atomic %].

FIG. 46(C) shows a cross-sectional EDX mapping image of Ga atoms, andFIG. 46(G) shows a plan-view EDX mapping image of Ga atoms. In the EDXmapping image in FIG. 46(C), the proportion of the Ga atoms in all theatoms is in the range of 8.23 to 31.95 [atomic %]. In the EDX mappingimage in FIG. 46(G), the proportion of the Ga atoms in all the atoms isin the range of 8.21 to 28.86 [atomic %].

FIG. 46(D) shows a cross-sectional EDX mapping image of Zn atoms, andFIG. 46(H) shows a plan-view EDX mapping image of Zn atoms. In the EDXmapping image in FIG. 46(D), the proportion of the Zn atoms in all theatoms is in the range of 5.37 to 25.92 [atomic %]. In the EDX mappingimage in FIG. 46(H), the proportion of the Zn atoms in all the atoms isin the range of 7.86 to 24.36 [atomic %].

Note that FIG. 46(A), FIG. 46(B), FIG. 46(C), and FIG. 46(D) show thesame region in the cross section of Sample 3J. FIG. 46(E), FIG. 46(F),FIG. 46(G), and FIG. 46(H) show the same region in the plane of Sample3J.

In FIG. 46(A), a group of laterally grown crystals is clearly observed,and in FIG. 46(E), crystals having a hexagonal structure with an angleof 120° are observed.

The EDX mapping images of the In atoms and the Zn atoms in FIG. 46(B)and FIG. 46(D) show particularly bright spots aligned as indicated bywhite lines. In FIG. 46(F) and FIG. 46(H), these lines form an angle ofapproximately 120°, which is characteristic of the hexagonal structure,and in FIG. 46(B) and FIG. 46(D), the same layered arrangement as inFIG. 46(A) can be observed. As shown in FIG. 46(C) and FIG. 46(G), sucha tendency is not observed for Ga atoms.

The resolution of EDX is generally affected by the regularity of atomicarrangement. When atoms are regularly arranged as in a single crystal,the atoms are arranged linearly in the beam incident direction, andincident electrons are therefore channeled and propagated along the atomrows. Thus, atomic columns can be separated. In contrast, when theregularity of atomic arrangement is low, the atom rows are out ofalignment and incident electrons are therefore scattered without beingchanneled. That is, the spatial resolution is low and an obtained imageis in a blurred state in some cases.

That is, since the crystallinity of CAAC is not as high as that ofsingle crystal, a beam is broadened and the resolution of EDX mapping isnot as high as that of HAADF-STEM; thus, CAAC is probably observed in ablurred state. From FIG. 44 , CAC is blurred because of a broadenedbeam; thus, the atoms are determined to be nanoparticles with a blurryboundary.

As described above, it is confirmed that the CAC-IGZO has a structuredifferent from that of an IGZO compound in which metal elements areevenly distributed, and has characteristics different from those of theIGZO compound. That is, it was confirmed that in the CAC-IGZO, regionsincluding GaO_(X3) or the like as a main component and regions includingIn_(X2)Zn_(Y2)O_(Z2) or InO_(X1) as a main component were separated toform a mosaic pattern.

Accordingly, it can be expected that when CAC-IGZO is used for asemiconductor element, the property derived from GaO_(X3) or the likeand the property derived from In_(X2)Zn_(Y2)O_(Z2) or InO_(X1)complement each other, whereby high on-state current (I_(on)), highfield-effect mobility (μ), and low off-state current (I_(off)) can beachieved. A semiconductor element including CAC-IGZO has highreliability. Thus, CAC-IGZO is suitably used in a variety ofsemiconductor devices typified by a display.

At least part of this example can be implemented in combination with anyof the embodiments and the other examples described in thisspecification as appropriate.

Example 4

In this example, the transistor 150 including the metal oxide 108 of oneembodiment of the present invention was fabricated and subjected totests for electrical characteristics and reliability. In this example,nine transistors, i.e., Sample 4A, Sample 4B, Sample 4C, Sample 4D,Sample 4E, Sample 4F, Sample 4G, Sample 4H, and Sample 4J, werefabricated as the transistor 150 including the metal oxide 108.

<Structure of Samples and Fabrication Method Thereof>

Sample 4A, Sample 4B, Sample 4C, Sample 4D, Sample 4E, Sample 4F, Sample4G, Sample 4H, and Sample 4J relating to one embodiment of the presentinvention will be described below. As Sample 4A to Sample 4J, thetransistors 150 having the structure illustrated in FIG. 7 werefabricated by the fabrication method described in Embodiment 2 withreference to FIG. 9 to FIG. 11 .

Sample 4A to Sample 4J were fabricated at different temperatures anddifferent oxygen flow rate ratios in film formation of the metal oxide108. The temperatures and the oxygen flow rate ratios in film formationof the metal oxides of Sample 4A to Sample 4J are shown in the followingtable.

TABLE 5 Formation condition of metal oxide 108 O₂ Formation Flow rate[sccm] ratio temperature O₂ Ar [%] [° C.] Sample 4A 30 270 10 R.T.Sample 4B 90 210 30 R.T. Sample 4C 150 150 50 R.T. Sample 4D 30 270 10130 Sample 4E 90 210 30 130 Sample 4F 150 150 50 130 Sample 4G 30 270 10170 Sample 4H 90 210 30 170 Sample 4J 150 150 50 170

The samples were fabricated by the fabrication method described inEmbodiment 2. The metal oxide 108 was formed using a metal oxide target(In:Ga:Zn=1:1:1.2 [atomic ratio]).

The transistor 150 had a channel length of 2 μm and a channel width of 3μm (hereinafter, also referred to as L/W=2/3 μm).

<I_(d)-V_(g) Characteristics of Transistor>

Next, I_(d)-V_(g) characteristics of the transistors (L/W=2/3 μm) inSample 4A to Sample 4J fabricated above were measured. As conditions formeasuring the I_(d)-V_(g) characteristics of each transistor, a voltageapplied to the conductive film 112 serving as a first gate electrode(hereinafter, the voltage is also referred to as gate voltage (V_(g)))and a voltage applied to the conductive film 106 serving as a secondgate electrode (hereinafter, the voltage is also referred to as backgate voltage (V_(bg))) were changed from −10 V to +10 V in increments of0.25 V. A voltage applied to the conductive film 120 a serving as asource electrode (the voltage is also referred to as source voltage(V_(s))) was 0 V (comm), and a voltage applied to the conductive film120 b serving as a drain electrode (the voltage is also referred to asdrain voltage (V_(d))) was 0.1 V and 20 V.

FIG. 47 shows the results of I_(d)-V_(g) characteristics andfield-effect mobilities of Sample 4A to Sample 4J. The solid line andthe dashed-dotted line represent I_(d) at V_(d)=20 V and I_(d) atV_(d)=0.1 V, respectively. The dashed line and the dotted line representfield-effect mobility calculated from a value measured at V_(d)=20 V andfield-effect mobility calculated from a value measured at V_(d)=0.1 V,respectively. In FIG. 47 , the first vertical axis represents I_(d) [A],the second vertical axis represents field-effect mobility (μFE)[cm²/Vs], and the horizontal axis represents V_(g) [V].

FIG. 47 shows that the transistors 150 of Sample 4A to Sample 4J havenormally-off characteristics. As shown in FIG. 47 , it was found thatSample 4A to Sample 4J have different on-state currents (I_(on)) anddifferent field-effect mobilities, particularly different field-effectmobilities in saturation regions. In particular, the maximum saturationmobilities and the rising characteristics of the field-effect mobilitiesaround 0 V were found to differ distinctly.

It was found from FIG. 47 that as the substrate temperature at the timeof film formation is lower or the oxygen flow rate ratio at the time offilm formation is lower, the field-effect mobility at low V_(g) issignificantly higher. In particular, Sample 4A was found to have amaximum field-effect mobility close to 40 cm²/Vs. The high mobility atlow V_(g) is suitable for high-speed driving at low voltage; therefore,application to a variety of semiconductor devices typified by a displaycan be expected.

From FIG. 47 , different behavior of field-effect mobility was found atV_(d)=20 V (shown by dashed lines) and V_(d)=0.1 V (shown by dottedlines). As V_(g) is increased, the field-effect mobility measured atV_(d)=20 V (shown by dashed lines) becomes higher. This is considered asan influence of heat generation of the transistor. Meanwhile, thefield-effect mobility measured at V_(d)=0.1 V (shown by dotted lines) ina high V_(g) range substantially coincides with an ideal saturationmobility curve calculated by the above formula (5).

At least part of this example can be implemented in combination with anyof the embodiments and the other examples described in thisspecification as appropriate.

Example 5

In this example, the analysis results of elements included in a samplewill be described. For the analysis, by energy dispersive X-rayspectroscopy (EDX), an EDX mapping image of a metal oxide film of oneembodiment of the present invention formed over a substrate is obtainedand evaluated. An energy dispersive X-ray spectrometer Analysis StationJED-2300T manufactured by JEOL Ltd. was used as an elementary analysisapparatus in the EDX measurement. A Si drift detector was used to detectan X-ray emitted from the sample.

<Structure of Samples and Fabrication Method Thereof>

In this example, Sample 5A was fabricated. Sample 5A includes asubstrate and a metal oxide over the substrate.

Next, a method for fabricating the sample will be described.

A glass substrate was used as the substrate. Over the substrate, a100-nm-thick In—Ga—Zn metal oxide was formed as a metal oxide with asputtering apparatus. The formation conditions were as follows: thepressure in a chamber was 0.6 Pa; an atmosphere using an Ar gas at aflow rate of 270 sccm and an O₂ gas at a flow rate of 30 sccm wasemployed as sputtering gases; and a metal oxide target (In:Ga:Zn=4:2:4.1[atomic ratio]) was used as a target. The metal oxide target provided inthe sputtering apparatus was supplied with an AC power of 2500 W, sothat the metal oxide film was formed.

Through the above steps, Sample 5A of this example was fabricated.

<Measurement Results>

In the EDX measurement, an EDX spectrum of a point is obtained in such amanner that electron beam irradiation is performed on the point in adetection target region of a sample, and the energy of characteristicX-ray of the sample generated by the irradiation and its frequency aremeasured. In this example, peaks of an EDX spectrum of the point areattributed to electron transition to the L shell in an In atom, electrontransition to the K shell in a Ga atom, and electron transition to the Kshell in a Zn atom and the K shell in an O atom, and the proportions ofthe atoms in the point are calculated. An EDX mapping image indicatingdistributions of proportions of atoms can be obtained through theprocess in an analysis target region of a sample.

FIG. 48 shows measurement results of a cross section of Sample 5A. FIG.48(A) shows a cross-sectional TEM image, and FIG. 48(B) and FIG. 48(C)show cross-sectional EDX mapping images. In the EDX mapping images, theproportion of an element is indicated by grayscale: the more measuredelements exist in a region, the brighter the region is; the lessmeasured elements exist in a region, the darker the region is. Themagnification of the EDX mapping images in FIG. 48 is 7,200,000 times.Note that FIG. 48(A), FIG. 48(B), and FIG. 48(C) show the same region inthe cross section of Sample 5A.

FIG. 48(B) shows a cross-sectional EDX mapping image of In atoms. In theEDX mapping image in FIG. 48(B), the proportion of the In atoms in allthe atoms is the range of 12.11 to 40.30 [atomic %]. FIG. 48(C) shows across-sectional EDX mapping image of Ga atoms. In the EDX mapping imagein FIG. 48(C), the proportion of the Ga atoms in all the atoms is in therange of 0.00 to 13.18 [atomic %].

The EDX mapping images in FIG. 48(B) and FIG. 48(C) show relativedistribution of bright and dark areas, indicating that the In atoms andthe Ga atoms have distributions in Sample 5A. Here, five regionssurrounded by black lines (a region 901, a region 902, a region 903, aregion 904, and a region 905) were extracted among regions whoseluminance is greater than or equal to 75% of the maximum luminance inFIG. 48(B). Five regions surrounded by dashed lines (a region 906, aregion 907, a region 908, a region 909, and a region 910) were extractedamong regions whose luminance is greater than or equal to 75% of themaximum luminance in FIG. 48(C). Five regions surrounded by white lines(a region 911, a region 912, a region 913, a region 914, and a region915) were extracted among regions whose luminance is greater than orequal to 25% and less than or equal to 75% of the maximum luminance inFIG. 48(B), and among regions whose luminance is greater than or equalto 25% and less than or equal to 75% of the maximum luminance in FIG.48(C).

In other words, the region 901 to the region 905 are regions including arelatively large number of In atoms. The region 906 to the region 910are regions including a relatively large number of Ga atoms. The region911 to the region 915 are regions including an average number of Inatoms and Ga atoms.

Regions including a relatively large number of Ga atoms, that is, thefive regions surrounded by the dashed lines (the region 906, the region907, the region 908, the region 909, and the region 910) in FIG. 48(C)were found to be relatively dark in FIG. 48(B). That is, the regionincluding a relatively large number of Ga atoms is expected to include arelatively small number of In atoms.

The proportions of elements in the region 901 to the region 915 in FIG.48(B) are shown in FIG. 48(D). The regions surrounded by the black lines(the region 901, the region 902, the region 903, the region 904, and theregion 905) were found to include a relatively large number of In atomsand a relatively small number of Ga atoms. The regions surrounded by thedashed lines (the region 906, the region 907, the region 908, the region909, and the region 910) were found to include a relatively small numberof In atoms and a relatively large number of Ga atoms.

FIG. 49 shows measurement results of a plane of Sample 5A. FIG. 49(A)shows a plan-view TEM image, and FIG. 49(B) and FIG. 49(C) showplan-view EDX mapping images. Note that FIG. 49(A), FIG. 49(B), and FIG.49(C) show the same region in the plane of Sample 5A.

FIG. 49(B) shows a plan-view EDX mapping image of In atoms. In the EDXmapping image in FIG. 49(B), the proportion of the In atoms in all theatoms is the range of 12.11 to 43.80 [atomic %]. FIG. 49(C) shows aplan-view EDX mapping image of Ga atoms. In the EDX mapping image inFIG. 49(C), the proportion of the Ga atoms in all the atoms is in therange of 0.00 to 14.83 [atomic %].

The EDX mapping images in FIG. 49(B) and FIG. 49(C) show relativedistribution of bright and dark areas, indicating that the In atoms andthe Ga atoms have distributions in Sample 5A. Here, five regionssurrounded by black lines (a region 921, a region 922, a region 923, aregion 924, and a region 925) were extracted among regions whoseluminance is greater than or equal to 75% of the maximum luminance inFIG. 49(B). Five regions surrounded by dashed lines (a region 926, aregion 927, a region 928, a region 929, and a region 930) were extractedamong regions whose luminance is greater than or equal to 75% of themaximum luminance in FIG. 49(C). Five regions surrounded by white lines(a region 931, a region 932, a region 933, a region 934, and a region935) were extracted among regions whose luminance is greater than orequal to 25% and less than or equal to 75% of the maximum luminance inFIG. 49(B), and among regions whose luminance is greater than or equalto 25% and less than or equal to 75% of the maximum luminance in FIG.49(C).

Regions including a relatively large number of Ga atoms, that is, thefive regions surrounded by the dashed lines (the region 926, the region927, the region 928, the region 929, and the region 930) in FIG. 49(C)were found to be relatively dark in FIG. 49(B). That is, the regionincluding a relatively large number of Ga atoms is expected to include arelatively small number of In atoms.

The proportions of elements in the region 921 to the region 935 in FIG.49(B) are shown in FIG. 49(D). The regions surrounded by the black lines(the region 921, the region 922, the region 923, the region 924, and theregion 925) were found to include a relatively large number of In atomsand a relatively small number of Ga atoms. The regions surrounded by thedashed lines (the region 926, the region 927, the region 928, the region929, and the region 930) were found to include a relatively small numberof In atoms and a relatively large number of Ga atoms.

As shown in FIG. 48(D) and FIG. 49(D), it was found that the In atomswere distributed in a range of higher than or equal to 25 atomic % andlower than or equal to 60 atomic %. Furthermore, it was found that theGa atoms were distributed in a range of higher than or equal to 3 atomic% and lower than or equal to 40 atomic %.

A region including a relatively large number of In atoms can be expectedto have relatively high conductivity. In contrast, a region including arelatively large number of Ga atoms can be expected to have a relativelyhigh insulating property. Accordingly, it is considered that carriersflow through the region including a relatively large number of In atoms,so that the conductivity property is exhibited and high field-effectmobility (μ) is achieved. Meanwhile, it is considered that distributingthe region including a relatively large number of Ga atoms in the metaloxide probably reduces leakage current and achieves favorable switchingoperation.

In other words, when a metal oxide having a CAC composition is used in asemiconductor element, the insulating property derived from a Ga atom orthe like and the conductivity derived from an In atom complement eachother, whereby high on-state current (I_(on)) and high field-effectmobility (μ) can be achieved.

At least part of this example can be implemented in combination with anyof the embodiments and the other examples described in thisspecification as appropriate.

Example 6

In this example, the transistor 150 including the metal oxide 108 of oneembodiment of the present invention was fabricated and the density ofdefect states was measured. In this example, nine transistors, i.e.,Sample 6A, Sample 6B, Sample 6C, Sample 6D, Sample 6E, Sample 6F, Sample6G, Sample 6H, and Sample 6J, were fabricated as the transistor 150including the metal oxide 108.

<Structure of Samples and Fabrication Method Thereof>

Sample 6A to Sample 6J relating to one embodiment of the presentinvention will be described below. As Sample 6A to Sample 6J, thetransistors 150 having the structure illustrated in FIG. 7 werefabricated by the fabrication method described in Embodiment 2 withreference to FIG. 9 to FIG. 11 .

Sample 6A to Sample 6J were fabricated at different temperatures anddifferent oxygen flow rate ratios in film formation of the metal oxide108. The metal oxide 108 was formed using a metal oxide target(In:Ga:Zn=1:1:1.2 [atomic ratio]). The temperatures and the oxygen flowrate ratios in film formation of the metal oxides of Sample 6A to Sample6J are shown in the following table.

TABLE 6 O₂ Formation Flow rate [sccm] ratio temperature O₂ Ar [%] [° C.]Sample 6A 30 270 10 R.T. Sample 6B 90 210 30 R.T. Sample 6C 150 150 50RT. Sample 6D 30 270 10 130 Sample 6E 90 210 30 130 Sample 6F 150 150 50130 Sample 6G 30 270 10 170 Sample 6H 90 210 30 170 Sample 6J 150 150 50170

The samples were fabricated by the fabrication method described inEmbodiment 2.

The transistor 150 had a channel length of 2 μm and a channel width of 3(hereinafter, also referred to as L/W=2/3 μm) or a channel length of 2μm and a channel width of 50 μm (hereinafter, also referred to asL/W=2/50 μm).

<Measurement of Shallow Defect States Using Transistor Characteristics>

[Measurement Method of Density of Shallow Defect States]

Shallow defect states (hereinafter, also referred to as sDOS) of a metaloxide can be estimated from electrical characteristics of a transistorin which the metal oxide was used as a semiconductor. In the followingdescription, the density of interface states of the transistor wasmeasured; and a method for estimating subthreshold leakage current inconsideration of the density of interface states and the number ofelectrons trapped by the interface states, N_(trap) is described.

The number of electrons trapped by the interface states, N_(trap), canbe measured by, for example, comparing drain current-gate voltage(I_(d)-V_(g)) characteristics of the transistor that were actuallymeasured and drain current-gate voltage (I_(d)-V_(g)) characteristicsthat were calculated.

FIG. 50 shows ideal I_(d)-V_(g) characteristics obtained by calculationand the actually measured I_(d)-V_(g) characteristics of the transistorwhen a source voltage V_(s) is 0 V and a drain voltage V_(d) is 0.1 V.Note that only values more than or equal to 1×10⁻¹³ A at which draincurrent I_(d) can be easily measured were plotted among the measurementresults of the transistor.

A change of the drain current I_(d) with respect to the gate voltageV_(g) is more gradual in the actually measured I_(d)-V_(g)characteristics than in the ideal I_(d)-V_(g) characteristics obtainedby calculation. This is probably because an electron is trapped by ashallow interface state positioned near energy at the conduction bandminimum (represented as Ec). In this measurement, the density ofinterface states N_(it) can be estimated more accurately inconsideration of the number of electrons (per unit area and unit energy)trapped by shallow interface states, N_(trap), with use of the Fermidistribution function.

First, a method for evaluating the number of electrons trapped byinterface trap states, N_(trap), by using schematic I_(d)-V_(g)characteristics illustrated in FIG. 51 is described. The dashed lineindicates ideal I_(d)-V_(g) characteristics without trap state which areobtained by the calculation. On the dashed line, a change in gatevoltage V_(g) when the drain current changes from I_(d)1 to I_(d)2 isrepresented by ΔV_(id). The solid line indicates the actually measuredI_(d)-V_(g) characteristics. On the solid line, a change in gate voltageV_(g) when the drain current changes from I_(d)1 to I_(d)2 isrepresented by ΔV_(ex). The potential at the target interface when thedrain current is I_(d)1, the potential at the target interface when thedrain current is I_(d)2, and the amount of change are represented byϕ_(it1), ϕ_(it2), and Δϕ_(it), respectively.

The slope of the actually measured values is smaller than that of thecalculated values in FIG. 51 , which indicates that ΔV_(ex) is alwayslarger than ΔV_(id). Here, a difference between ΔV_(ex) and ΔV_(id)corresponds to a potential difference that is needed for trapping of anelectron in a shallow interface state. Therefore, ΔQ_(trap) which is theamount of change in charge due to trapped electrons can be expressed bythe following formula (6).[Formula 6]ΔQ _(trap) =−C _(tg)(ΔV _(ex) −ΔV _(id))  (6)

C_(tg) is combined capacitance of an insulator and a semiconductor perunit area. In addition, ΔQ_(trap) can be expressed by the formula (7) byusing the number of trapped electrons N_(trap) (per unit area and perunit energy). Note that q represents elementary charge.[Formula 7]ΔQ _(trap) =−qN _(trap)Δϕ_(it)  (7)

Simultaneously solving the formulae (6) and (7) gives the formula (8).[Formula 8]−C _(tg)(ΔV _(ex) −ΔV _(id))=−qN _(trap)Δϕ_(it)  (8)

Then, taking the limit zero of Δϕ_(it) in the formula (8) gives theformula (9).

$\begin{matrix}\left\lbrack {{Formula}9} \right\rbrack &  \\{N_{trap} = {{\frac{C_{tg}}{q}{\lim\limits_{{\Delta\phi_{it}}\rightarrow 0}\left( {\frac{\Delta V_{ex}}{{\Delta\phi}_{it}} - \frac{\Delta V_{id}}{{\Delta\phi}_{it}}} \right)}} = {C_{tg}\left( {\frac{\partial V_{ex}}{\partial\phi_{it}} - \frac{\partial V_{id}}{\partial\phi_{it}}} \right)}}} & (9)\end{matrix}$

In other words, the number of electrons trapped by an interface,N_(trap), can be estimated by using the ideal I_(d)-V_(g)characteristics, the actually measured I_(d)-V_(g) characteristics, andthe formula (9). Note that the relationship between the drain currentand the potential at the interface can be obtained by the abovecalculations.

The relationship between the number of electrons N_(trap) per unit areaand per unit energy and the density of interface states N_(it) isexpressed by the formula (10).

$\begin{matrix}\left\lbrack {{Formula}10} \right\rbrack &  \\{N_{trap} = {\frac{\partial}{\partial\phi_{it}}{\int_{- \infty}^{\infty}{{N_{it}(E)}{f(E)}dE}}}} & (10)\end{matrix}$

Here, f(E) is Fermi distribution function. The N_(trap) obtained fromthe formula (9) is fitted with the formula (10) to determine N_(it). Theconduction characteristics including I_(d)<0.1 pA can be obtained by thedevice simulator to which the N_(it) is set.

The actually measured I_(d)-V_(g) characteristics in FIG. 50 are appliedto the formula (9) and the results of extracting N_(trap) are plotted aswhite circles in FIG. 52 . The vertical axis in FIG. 52 represents Fermienergy Ef at the conduction band minimum Ec of a semiconductor. Thehorizontal axis in FIG. 52 represents the density of states. The maximumvalue is positioned on the dashed line just under Ec. When taildistribution of the formula (11) is assumed as N_(it) of the formula(10), N_(trap) can be fitted well like the dashed line in FIG. 52 . As aresult, the trap density at an end of the conduction bandN_(ta)=1.67×10¹³ cm⁻² eV and the characteristic decay energyW_(ta)=0.105 eV are obtained as the fitting parameters.

$\begin{matrix}\left\lbrack {{Formula}11} \right\rbrack &  \\{{N_{it}(E)} = {N_{ta}{\exp\left\lbrack \frac{E - E_{c}}{W_{ta}} \right\rbrack}}} & (11)\end{matrix}$

FIG. 53(A) and FIG. 53(B) show the inverse calculation results ofI_(d)-V_(g) characteristics by feeding back the obtained fitting curveof interface state to the calculation using the device simulator. FIG.53(A) shows the calculated I_(d)-V_(g) characteristics when the drainvoltage V_(d) is 0.1 V and 1.8V and the actually measured I_(d)-V_(g)characteristics when the drain voltage V_(d) is 0.1 V and 1.8V. FIG.53(B) is a graph in which the drain current I_(d) is a logarithm in FIG.53(A).

The curve obtained by the calculation substantially matches with theplot of the actually measured values, which suggests that the calculatedvalues and the measured values are highly reproducible. Thus, the abovemethod is quite appropriate as a method for calculating the density ofshallow defect states.

[Measurement Results of Density of Shallow Defect States]

Next, the density of shallow defect states of Sample 6A, Sample 6B,Sample 6C, Sample 6D, Sample 6E, Sample 6F, Sample 6G, Sample 6H, andSample 6J were measured by comparing measured electrical characteristicswith ideal calculation values according to the above-described method.

FIG. 54 shows calculated average density of shallow defect states ofSample 6A, Sample 6B, Sample 6C, Sample 6D, Sample 6E, Sample 6F, Sample6G, Sample 6H, and Sample 6J.

As shown in FIG. 54 , the sample formed at a lower oxygen flow rateratio in film formation of the metal oxide 108 or a lower temperature infilm formation of the metal oxide 108 has a lower peak density ofshallow defect states.

As described above, Sample 6A to Sample 6J were found to be transistorseach including a metal oxide film with a low density of defect states.It is presumed that the oxygen-transmitting property is improved becausethe metal oxide film is formed at a low temperature and a low oxygenflow rate ratio, and that the amount of diffused oxygen in thefabrication process of the transistor is increased, whereby the amountof defects such as oxygen vacancies in the metal oxide film and at theinterface between the metal oxide film and the insulating film isreduced.

At least part of this example can be implemented in combination with anyof the embodiments and the other examples described in thisspecification as appropriate.

Example 7

In this example, the transistor 150 including the metal oxide 108 of oneembodiment of the present invention was fabricated and the density ofdefect states was measured. In this example, nine transistors, i.e.,Sample 7A, Sample 7B, Sample 7C, Sample 7D, Sample 7E, Sample 7F, Sample7G, Sample 7H, and Sample 7J, were fabricated as the transistor 150including the metal oxide 108.

<Structure of Samples and Fabrication Method Thereof>

Sample 7A to Sample 7J relating to one embodiment of the presentinvention will be described below. As Sample 7A to Sample 7J, thetransistors 150 having the structure illustrated in FIG. 7 werefabricated by the fabrication method described in Embodiment 2 withreference to FIG. 9 to FIG. 11 .

Sample 7A to Sample 7J were fabricated at different temperatures anddifferent oxygen flow rate ratios in film formation of the metal oxide108. The metal oxide 108 was formed using a metal oxide target(In:Ga:Zn=4:2:4.1 [atomic ratio]). The temperatures and the oxygen flowrate ratios in film formation of the metal oxides of Sample 7A to Sample7J are shown in the following table.

TABLE 7 O₂ Formation Flow rate [sccm] ratio temperature O₂ Ar [%] [° C.]Sample 7A 30 270 10 R.T. Sample 7B 90 210 30 R.T. Sample 7C 300 0 100R.T. Sample 7D 30 270 10 130 Sample 7E 90 210 30 130 Sample 7F 300 0 100130 Sample 7G 30 270 10 170 Sample 7H 90 210 30 170 Sample 7J 300 0 100170

The samples were fabricated by the fabrication method described inEmbodiment 2.

The transistor 150 had a channel length of 2 μm and a channel width of 3(hereinafter, also referred to as L/W=2/3 μm) or a channel length of 2μm and a channel width of 50 μm (hereinafter, also referred to asL/W=2/50 μm).

<Measurement of Shallow Defect States Using Transistor Characteristics>

[Measurement Method of Density of Shallow Defect States]

Shallow defect states of the metal oxide 108 was estimated fromelectrical characteristics of a transistor in which the metal oxide wasused as a semiconductor. The calculation method was similar to thatdescribed in the above example. The density of interface states of thetransistor was measured, and subthreshold leakage current was estimatedin consideration of the density of interface states and the number ofelectrons trapped by the interface states, N_(trap).

[Measurement Results of Density of Shallow Defect States]

Next, the density of shallow defect states of Sample 7A, Sample 7B,Sample 7C, Sample 7D, Sample 7E, Sample 7F, Sample 7G, Sample 7H, andSample 7J were measured by comparing measured electrical characteristicswith ideal calculation values according to the above-described method.

FIG. 55 shows calculated average density of shallow defect states ofSample 7A, Sample 7B, Sample 7C, Sample 7D, Sample 7E, Sample 7F, Sample7G, Sample 7H, and Sample 7J.

As shown in FIG. 55 , the sample formed at a lower oxygen flow rateratio in film formation of the metal oxide 108 or a lower temperature infilm formation of the metal oxide 108 has a lower peak density ofshallow defect states.

As described above, Sample 7A to Sample 7J were found to be transistorseach including a metal oxide film with a low density of defect states.It is presumed that the oxygen-transmitting property is improved becausethe metal oxide film is formed at a low temperature and a low oxygenflow rate ratio, and that the amount of diffused oxygen in thefabrication process of the transistor is increased, whereby the amountof defects such as oxygen vacancies in the metal oxide film and at theinterface between the metal oxide film and the insulating film isreduced.

At least part of this example can be implemented in combination with anyof the embodiments and the other examples described in thisspecification as appropriate.

Example 8

In this example, the transistor 150 including the metal oxide 108 of oneembodiment of the present invention was fabricated and subjected totests for electrical characteristics and reliability. In this example, atransistor of Sample 8A was fabricated as the transistor 150 includingthe metal oxide 108.

<Structure of Samples and Fabrication Method Thereof>

Sample 8A relating to one embodiment of the present invention will bedescribed below. As Sample 8A, the transistor 150 having the structureillustrated in FIG. 7 was fabricated by the fabrication method describedin Embodiment 2 with reference to FIG. 9 to FIG. 11 .

The temperature and the oxygen flow rate ratio in film formation of themetal oxide 108 of Sample 8A are shown in the following table.

TABLE 8 O₂ Formation Flow rate [sccm] ratio temperature O₂ Ar [%] [° C.]Sample 8A 0 300 0 R.T.

Sample 8A was fabricated by the fabrication method described inEmbodiment 2. The metal oxide 108 was formed using a metal oxide target(In:Ga:Zn=5:1:7 [atomic ratio]).

The transistor 150 had a channel length of 3 μm and a channel width of50 μm (hereinafter, also referred to as L/W=3/50 μm).

<I_(a)- V_(g) Characteristics of Transistor>

Next, I_(d)-V_(g) characteristics of the transistor (L/W=3/50 μm) inSample 8A fabricated above were measured. As conditions for measuringthe I_(d)-V_(g) characteristics of each transistor, a voltage applied tothe conductive film 112 serving as a first gate electrode (hereinafter,the voltage is also referred to as gate voltage (V_(g))) and a voltageapplied to the conductive film 106 serving as a second gate electrode(hereinafter, the voltage is also referred to as back gate voltage(V_(bg))) were changed from −10 V to +10 V in increments of 0.25 V. Avoltage applied to the conductive film 120 a serving as a sourceelectrode (the voltage is also referred to as source voltage (Vs)) was 0V (comm), and a voltage applied to the conductive film 120 b serving asa drain electrode (the voltage is also referred to as drain voltage(V_(d))) was 0.1 V and 20 V.

FIG. 56 shows the results of I_(d)-V_(g) characteristics andfield-effect mobilities of Sample 8A. The solid line and thedashed-dotted line represent I_(d) at V_(d)=20 V and I_(d) at V_(d)=0.1V, respectively. The dashed line represents field-effect mobility. InFIG. 56 , the first vertical axis represents I_(d) [A], the secondvertical axis represents field-effect mobility (μFE) [cm²/Vs], and thehorizontal axis represents V_(g) [V]. The field-effect mobility wascalculated from the value measured at V_(d)=20 V.

Note that in FIG. 56 , measurement was performed with the upper limit ofI_(d) in the measurement set to 1 mA. In FIG. 56 , when V_(d) is 20 V,I_(d) exceeds this upper limit at V_(g)=7.5 V. For this reason, FIG. 56shows the field-effect mobility in the range where V_(g) is lower thanor equal to 7.5 V as the field-effect mobility estimated from suchI_(d)-V_(g) characteristics.

As shown in FIG. 56 , the transistor of this example has favorableelectrical characteristics. Here, Table 9 shows the characteristics ofthe transistor shown in FIG. 56 .

TABLE 9 S Ioff μFE(@Vg = μFE(max)/ μFE(max) Vth [V/ [A/ 2 V) μFE(@Vg =[cm²V⁻¹s⁻¹] [V] decade] cm²] [cm²V⁻¹s⁻¹] 2 V) 103 −0.1 0.12 <1 × 10⁻¹²70 1.47

As described above, the field-effect mobility of the transistor of thisexample exceeds 100 cm²/Vs. This field-effect mobility is equivalent tothat of a transistor including low-temperature polysilicon and meansextraordinary characteristics for a transistor using the metal oxide108.

As shown in Table 9, Sample 8A includes a first region where the maximumvalue of the field-effect mobility of the transistor at a gate voltagehigher than 0 V and lower than or equal to 10 V is larger than or equalto 60 cm²/Vs and smaller than 150 cm²/Vs, a second region where thethreshold voltage is higher than or equal to −1 V and lower than orequal to 1 V, a third region where the S value is smaller than 0.3V/decade, and a fourth region where the off-state current is lower than1×10⁻¹² A/cm², and μ_(FE)(max)/μ_(FE)(V_(g)=2 V) is larger than or equalto 1 and smaller than 2 where μ_(FE)(max) represents the maximum valueof the field-effect mobility of the transistor and μ_(FE)(V_(g)=2 V)represents the value of the field-effect mobility of the transistor at agate voltage of 2 V.

The characteristics of the transistor can be obtained with the use ofthe metal oxide 108 described above. A transistor including the metaloxide 108 in its semiconductor layer can have both high carrier mobilityand excellent switching characteristics.

At least part of this example can be implemented in combination with anyof the embodiments and the other examples described in thisspecification as appropriate.

REFERENCE NUMERALS

-   001 region-   002 region-   100 transistor-   102 substrate-   104 insulating film-   106 conductive film-   108 metal oxide-   108 a metal oxide-   108 n region-   110 insulating film-   110_0 insulating film-   112 conductive film-   112_0 conductive film-   112_1 conductive film-   112_2 conductive film-   116 insulating film-   118 insulating film-   120 a conductive film-   120 b conductive film-   122 insulating film-   140 mask-   141 a opening-   141 b opening-   143 opening-   150 transistor-   160 transistor-   300A transistor-   300B transistor-   300C transistor-   300D transistor-   302 substrate-   304 conductive film-   306 insulating film-   307 insulating film-   308 metal oxide-   312 a conductive film-   312 b conductive film-   314 insulating film-   316 insulating film-   318 insulating film-   320 a conductive film-   320 b conductive film-   341 a opening-   341 b opening-   342 a opening-   342 b opening-   342 c opening-   600 display panel-   601 transistor-   604 connection portion-   605 transistor-   606 transistor-   607 connection portion-   612 liquid crystal layer-   613 conductive film-   617 insulating film-   620 insulating film-   621 insulating film-   623 conductive film-   631 coloring layer-   632 light-blocking film-   633 a alignment film-   633 b alignment film-   634 coloring layer-   635 conductive film-   640 liquid crystal element-   641 adhesive layer-   642 adhesive layer-   643 conductive film-   644 EL layer-   645 a conductive film-   645 b conductive film-   646 insulating film-   647 insulating film-   648 conductive film-   649 connection layer-   651 substrate-   652 conductive film-   653 semiconductor film-   654 conductive film-   655 opening-   656 polarizing plate-   659 circuit-   660 light-emitting element-   661 substrate-   662 display portion-   663 conductive film-   666 wiring-   672 FPC-   673 IC-   681 insulating film-   682 insulating film-   683 insulating film-   684 insulating film-   685 insulating film-   686 connector-   687 connector-   700 model-   702 local structure-   704 local structure-   706 local structure-   708 local structure-   710 local structure-   712 local structure-   901 region-   902 region-   903 region-   904 region-   905 region-   906 region-   907 region-   908 region-   909 region-   910 region-   911 region-   912 region-   913 region-   914 region-   915 region-   921 region-   922 region-   923 region-   924 region-   925 region-   926 region-   927 region-   928 region-   929 region-   930 region-   931 region-   932 region-   933 region-   934 region-   935 region

What is claimed is:
 1. A composite oxide comprising: a first region anda second region, wherein the composite oxide comprises a single-layerstructure, wherein the first region comprises In, Zn and an element M1,wherein the element M1 is one or more of Al, Ga, Si, B, Y, Ti, Fe, Ni,Ge, Zr, Mo, La, Ce, Nd, Hf, Ta, W, Mg, V, Be, and Cu, wherein the secondregion comprises In, Zn, and an element M2, wherein the element M2 isone or more of Al, Ga, Si, B, Y, Ti, Fe, Ni, Ge, Zr, Mo, La, Ce, Nd, Hf,Ta, W, Mg, V, Be, and Cu, wherein a proportion of the element M1 to In,Zn, and the element M1 in the first region is less than a proportion ofthe element M2 to In, Zn, and the element M2 in the second region,wherein a proportion of In to In, Zn, and the element M1 in the firstregion is more than a proportion of In to In, Zn, and the element M2 inthe second region, and wherein, when an analysis of the composite oxideby X-ray diffraction is performed, a diffraction pattern result in theX-ray diffraction has a peak whose shape is asymmetric with an angle atwhich a maximum intensity of the peak in X-ray diffraction is detectedas a symmetry axis.
 2. The composite oxide according to claim 1, whereinthe maximum intensity of the peak is detected between 2θ=30° and 2θ=35°.3. The composite oxide according to claim 1, wherein the element M1 andthe element M2 are Ga.
 4. The composite oxide according to claim 1,further comprising a region including a nanocrystal and a crystallineregion whose c-axis is aligned.
 5. The composite oxide according toclaim 1, wherein the first region or the second region comprises ananocrystal.
 6. The composite oxide according to claim 1, wherein thefirst region or the second region comprises a particle whose size isgreater than or equal to 0.5 nm and less than or equal to 10 nm.
 7. Thecomposite oxide according to claim 1, wherein the first region or thesecond region is not in an amorphous state, and wherein the first regionor the second region comprises a particle whose size is greater than orequal to 0.5 nm and less than or equal to 10 nm.
 8. The composite oxideaccording to claim 1, wherein a plurality of spots are observed in aring-shaped region in an electron diffraction pattern image of a part ofthe composite oxide.
 9. A semiconductor device comprising a transistor,the transistor comprising: the composite oxide according to claim 1; anda gate, a source, and a drain, wherein the composite oxide is used in achannel region in the transistor.
 10. The semiconductor device accordingto claim 9, wherein the transistor is provided in a pixel.
 11. Thesemiconductor device according to claim 9, wherein the transistor isprovided in a driver.
 12. The semiconductor device according to claim 9,wherein the transistor is provided in a gate driver.